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http://www.archive.org/details/proceedingsofsec25akad 


A KONINKLIJKE AKADEMIE 
VAN _WETENSCHAPPEN 


-- TE AMSTERDAM -:- 


fROCEEDINGS OF THE 
pee TION OF SCIENCES 


VOLUME XxXV 
— (Nos. 1—10) — 


146 
wy Areal 


PUBLISHED BY 
“KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN”, AMSTERDAM 
MARCH 1923 


. ‘ie ae ks m) 
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yi Dy, ‘a + rey ay, AF + it 
c\ ' / fs : ee) oe “4 ; od 7, a | L. Pe 


Tia | (Translated from: ,,Verslag van de Gewone Vergader 
Natuurkundige Afdeeling” Dl. XXXI). 


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Proceedings N°. 


CONTENTS. 


1 and 2 


Son andy 4: 


5) EhaNal (5 


. 7 and 8 


. 9 and 10 . 


229 


383 


KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN 
TE AMSTERDAM. 


PROCEEDINGS 


VOLUME XXV 


Nes, 1 and 2. 


President: Prof. F. A. F. C. WENT. 
Secretary: Prof. L. BOLkK. 


(Translated from: “Verslag van de gewone vergaderingen der Wis- en 


Natuurkundige Afdeeling,” Vol. XXXI). 


CONTENTS. 


P. EHRENFEST and G. BREIT: “A remarkable case of quantization”, p. 2. 

G. L. FUNKE: “The influence of hydrogen ion concentration upon the action of the amylase of 
Aspergillus niger’. (Communicated by Prof. F. A. F. C. WENT), p. 6. 

R. KR4USEL: ,Ueber einen fossilen Baumstamm von Bolang (Java), ein Beitrag zur Kenntnis der 

fossilen Flora Niederlandisch-Indiens”. (Communicated by Prof. J. W. MOLL), p.9. (Mit 1 Tafel). 

L. BOLK: “On the Significance of the Supra-orbital Ridges in the Primates”, p. 16. 

JAN DE VRIES: “Representation of a Bilinear Congruence of Twisted Cubics on a Bilinear Con- 
gruence of Rays”, p. 22. 

J. M. BIJVOET and A. KARSSEN: “Research by means of Rontgen-Rays on the Structure of the 
Crystals of Lithium and some of its Compounds with Light Elements. Il. Lithium-Hydride”. 
(Communicated by Prof. P. ZEEMAN), p. 27. 

J. W. JANZEN and L. K. WOLFF: “Studies about D’'HERELLE’s Bacteriophagus”. (Communicated by 
Prof. C, EYKMAN), p. 31. 

K. LANDSTEINER: “Experiments on Anaphylaxis with Azoproteins”. (Communicated by Prof. C. H. H. 
SPRONCK), p. 34. 

K. J. FERINGA: “On the Causes of the Emigration of Leukocytes”. (Communicated by Prof. H. J. 
HAMBURGER), p. 36. 


ROBERT F. GRIGGS: “Observations on the Incandescent Sand Flow of the Valley of ten thousand 


smokes”. p. 42. 
Erratum, p. 50. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Physics. — “A remarkable case of quantization.” By Prof. P. 
Enrenrest and G. Breit. 


(Communicated at the meeting of January 28, 1922). 


1. It is possible to indicate simple mechanical systems for which 
a formal application of the quantum rules gives well defined and 
yed apparently unreasonable stationary motions. Bonr’s Principle of 
Correspondence‘) offers an essentially new viewpoint for the treat- 
ment of these cases and will probably contribute to their complete 
solution. It will suffice to discuss a special case which is so chosen 
as to minimize the mathematical analysis. *) 


2. A rigid electric dipole. having a moment of inertia / is free 
to rotate in the Y, Y plane about its own midpoint. 

Let us suppose that by means of a suitable kinematical arrange- 
ment the rotating dipole is thrown back elastically as soon as the 
angle ~, which the dipole makes with the axis of X, reaches the 
boundaries of the interval 

SM Mt Es te ai Mic erate SS (1) 
where / is a large, in general an irrational number. Let an angular 
velocity w be given to the dipole. Its angular momentum is then 
p = /w and it executes a periodic motion with the pemod 


22 : : 


During the motion the dipole traverses. the interval (1) making 
in a period 2f complete revolutions to the right followed by the 
same number of revolutions to the left. In the motion the “qiast- 
periode” 

1) N. Bonr, Quantum theory of line-spectra- I, If Kopenhagen 1918. H. kee, 
Intensities of spectral lines. Kopenhagen 1919. 

2) A case which differs slightly from the one discussed in § 2, Saihely the case 
of a rigid dipole torsionally suspended by an elastic thread of small rigidity one 
of us submitted to Einstein for consideration as early as 1912 (with reference to 
the problem of quantization of Hy molecules — P. Enrenrest. Verh. d. D. Phys. 
Ges. 15, 451, 1913). lt was impossible however to settle the difffeulty here diseussed 
by the means- whieh -were-then-available. — -* = > = 


é|¥ 


(3) 


becomes noticeable. This period is a 4. part of 7’ and is equal to 
the time taken by the dipole to make a complete revolution through 
the angle 27. The projection of the moment of the dipole on a line 
in the plane X-Y-say on the axis of X depends on the time in the 
manner shown on the figure (for the sake of economy the “large 
number” 7 is here taken as being approximately 2). 


VN VU 


3. The quantum relation for our system is 


frag = nh Peaomromy wore! 1 % 


where the coordinate q is the angle g, p is the corresponding 
momentum | w and the integral is taken over a complete perid 7’. 
This gives in our case 


poccono 


Aen — Nn liey laptonasitis the Balfisei) 

or 

h 
Bf (6) 

If now the restricting boundary of the interval (1) is so chosen 
as to make jf very large, then the differences between consecutive 
values of p (see (6)) (and therefore also between consecutive values 
of the energy) are very small. 


P=Hn 


4. This result appears to be unacceptable. In fact if we pass to 
the limit of f= ie. if the restriction of the boundaries on the 
dipole disappears then equation (4) gives certainly 

‘ fof h x: 

2 STG et EC aR ae 
for now @ is the period. Here (Equ. (7)) p changes by finite steps 
whereas if the previous consideration be applied (Equ. (6)) the steps 
become infinitesimal for f=. This is the contradiction to be 
discussed. 


5. Bonr’s principle of correspondence offers a new point of view 
for the treatment of this case. As before let 7 be a very large 
1* 


- 


4 


number and suppose that the permissible values of p are truly 
given by Equ. (6). We want to know the requirements made by 
the principle of correspondence as to the “probability of a transition” 
from the state n = n, to the state n = n, (say as the result of absorption 
in a field of radition). The Principle of correspondence regards the 
probability of the transitions as analogous to the amplitudes of 
“corresponding” harmonics in a Fourier series expansion of the 
function represented graphically on the figure. This function repre- 
sents the dependence on the time of the Y or Y component of 
the dipole’s moment. The Fourier expansion of the function may 
be put into the form 


s 2 
eS rArcos (: =P oe) ST 
1 7 


The harmonics “corresponding” to the transition n,—>n, are 
given by: 
i eS ee  g] () 
From an inspection of the figure or by means of a short caleul- 
ation it becomes apparent that for a large value of / the amplitudes 
of all the harmonics are small with the exception of those harmonics 
whose period is nearly equal to the “quasiperiod” @ i.e. with the 
exception of those for which 


-50 .....) ee 


or 

3 ep ee ee 

Therefore if f is large all the transitions have a very small 
probability with the exception of those for which very nearly 


ny — Ny af eee ee 
and therefore (in virtue of (6)) 
eal ® h 
Pairs) Ta Vs he hema peer eh) 


which is the same as the interval between consecutive values of p 
prescribed by (7) for infinitely large values of /. 


6. If therefore we should take a collection of identical samples 
of our system having all the same very large value of f, being all 
at rest i.e. in the state p=O at the time ¢=O and if we should 
subject each sample independently to the action of a black body 
radiation — then we should find at a later time ¢ that: 

A. Out of the very dense succession of the p levels which are 


5 


permitted by (6) only those are occupied by an appreciable number 
of the systems which nearly coincide with the levels of p given 
by (7). 

B. The transitions which take place have almost without excep- 


jh 
tion the magnitude = (and not a multiple of it) (See (13)). This is 
at 


again in good agreement with the fact that for f= the Fovrimr 
expansion of the xz (or y) component contains only the fundamental 
and no higher harmonics so that for this case the Principle of 
Correspondence allows only the transitions (see (7)) for which 
ee, —— = A 


7. A question must now be mentioned the precise explanation of 
which would be of value. For the discussion of thermal equilibrium 
in our complex we must know the “weights” (the a priori proba- 
bility) to be ascribed to each p level. For f+ @ it would appear 
that the same weight should be given to every stop of (6) — in- 
dependently of the value of / and independently of the density 
with which the levels follow each other. On the other hand for 
f= only the levels given by (7) are to have a weight (the same 
for all). A closer examination of this case will probably make it 
necessary to consider the fact that we are concerned here with a 
double limit viz. im t= (the lapse of an infinitely long time for 
the establishment of thermal equilibrium) and hm f=; our dis- 
satisfaction is really based on an unconscious demand that the result 
should be independent of the order in which the two limits are 
approached. 

The junior author of the paper (G. Breit) is Fellow of the National 
Research council, United States of America. 


The University, Leiden. 


Botany. — “The influence of hydrogen ion concentration wpon the 
action of the amylase of Aspergillus niger”. By G. L. Funke. 
(Communicated by Prof. F. A. F. C. Wen7). 


(Communicated at the meeting of January 28, 1922). 


Aspergillus niger produces large quantities of amylase, part of 
which migrates into its nutritive surrounding. In the mean time the 
fungus forms acids which cause that medium to have a high hydrogen 
ion concentration. As this however seemed not to influence un- 
favourably the action of the amylase, the supposition was justified 
that the amylase of Aspergillus niger could not have its optimal 
action at the same hydrogen ion concentration as the ptyaline which 
works best at a nearly neutral or faintly acid reaction (4 and 5). 

Therefore I made a preliminary investigation in the way as 
has been indicated first by SérEnsen (1). Buffer solutions however 
were made according to the methods of Crark and Luss (7). 

Generally the same amounts of enzyme solution out of the 
nutritive liquid were mixed up with buffer solution and amylum 


enzyme 


1 Px 2 3 4 5 6 7 8 


solution 0.16°/,. The hydrogen ion concentration of this mixture 
was determined by aid of colorimetric indicators, the rate of 
hydrolysis of the amylum by the iodine reaction. 


7 


. Results. are. plotted into. the annexed curve (I). As can be seen 
there is no point of optimal action but a broad optimal zone 
extending from a Py of about. 3,5 till about 5,5. 

Neither the concentration of the amylase, nor the composition of 
the nutritive liquid appeared to have influence. The same results 
were obtained with amylase extracted from the mycelium. 

These results largely confirm the theory of Micuaéuis who con- 
siders the enzymes.as ampholytes (2 and 3). The form of the curve 
indeed is nearly identical to the dissociation rest curve of an amphotere 
electrolyte. According to his formulas 


Tee ts fee! 
(H) (OH) 
in which 9 =1— y= dissociation rest 
SS rate of dissociation 
Ge dissociation constant. of the acid 
ie dissociation constant of the base 


‘the points on the ordinate — half of the maximum height of the 
curve indicate the logarithms of the dissociation constants of acid 
‘and base on the abscissa. These are to be found at about 2,26 and 
6,2. So the dissociation constant of the acid would be —6.3  10~7, 
that of, the base = 2.884. 10-12, 


enzyme 


ur 
(99) 
) 
o 


We may consider in the same way curve II which represents 


8 


the influence of the hydrogen ion concentration upon the amylase 
of malt’). 

The dissociation constant of the acid appears to be the same as 
for the amylase of Aspergillus, that of the base on the contrary is 
bigger i.e. =—5.76 X 10—-". So as an acid the two amylases are 
equally strong, as a base that of the malt is the weakest. 

Further investigations on other sorts of amylase will perhaps 
instruct us, if pointing out their differences in this way will be of 
any value. 


Utrecht, November 1921. Botanical Laboratory. 


LITERATURE. 


1. SéreNsEN S. P. L., Biochem. Zeitschr. Bd. 21, 1909. Enzymstudien II. 

2. MicuAELIS, L., Biochem. Zeitschr. Band 33, 1911. Ueber die Dissoziation der 
amphoteren Electrolyte. 

3. MicHaELis L. und Davipsoun, Biochem. Zeitschr. Band 35, 1911. Die Wir- 
kung der H. Ionen auf das Invertin. 

4. Ringer, W. E. en Triat H. van, Onderzoek. Physiol. lab. der Un. Utrecht. 
5e reeks, dl. 14, 1913. Over den invloed van de reactie op de werking van ptyaline. 

5. MicHartis L. und Pecustein, H., Bioch. Zeitschr. Band 59, 1914. Die 
Wirkungsbedingungen der Speicheldiastase. 

6. Apter, L., Biochem. Zeitschr. Band 77, 1916. Ueber den Einfluss der Was- 
serstoffionen auf die Wirksamkeit der Malzdiastase. 

7. Crank, W. M. and Luss, H. Am., Journ. of Bact. Vol. II. 1917. The colori- 
metric determination of hydrogen ion concentration and its applications in bacteriology. 


1) It might be doubted if the iodine reaction method is accurate enough to get 
exact results. | therefore refer to those of ADLER (6) who determined the hydro- 
lysis of amylum by means of rotation and reductive power. The numbers he 
obtained appear to give a curve nearly identical to mine. 


Palaeontology. — ‘Ueber einen fossilen Baumstamm von Bolang 
(Java), ein Beitrag zur Kenntnis der fossilen Flora Nieder- 
liindisch-Indiens”. By Dr. R. Krauser. (Communicated by 
Prof. J. W. Mott.) 


(Communicated at the meeting of January 28, 1922). 


In der Sammlung des Mineralogisch-Geologischen Instituts der 
Reichsuniversitat zu Groningen befindet sich ein dusserlich sehr gut 
erhaltenes Stiick eines verkieselten Baumstammes von Bolang auf 
Java. Der Durchmesser des 23 cm langen Bruclistiickes betragt 
19—23 cm. Ueber Fundort u.s.w. gibt folgende Notiz Auskunft: 
»Fossiler Baumstamm (batoe sempoer), wie solche in verschiedener 
Groésze, bis 2 m lang und mit einem zuweilen 60 cm erreichen- 
den Durchmesser in Bolang auf Java gefunden werden. Sie kommen 
haufig auf der Oberflache oder im Fluszbette zerstrent vor, finden 
sich aber auch in 1—2 m Tiefe im Boden auf dem Kamm eines 
Hiigelzuges. (Empfangen von Herrn C. Barenps)’. Angaben iiber 
das geologische Alter der Fundschicht liegen nicht vor. 

Der von Herrn Prof. Dr. Bonnema, dem an dieser Stelle zu 
danken, mir eine angenehme Pflicht ist, ausgehenden Anregung 
zur Untersuchung des Holzes leistete ich um so lieber Folge, als es 
wiinschenswertes Vergleichsmaterial fiir eine gleichzeitig durchge- 
fiihrte Bearbeitung fossiler Hdlzer aus Sumatra bot, iiber die 
an anderer Stelle berichtet wird (KrAusen 1). Dort ist auch zu 
zeigen versucht worden, dasz die Behandlung derartiger Reste 
keineswegs nutzlos ist, selbst angesichts der zum Teil noch recht 
unvollkommenen Kenntnis vom anatomischen Bau der rezenten, 
tropischen Laubbaume. Gerade dieser Umstand verlangt aber eine 
moglichst ausfiihrliche Beschreibung der Fossilien. Nur dann_ ist 
eine brauchbare Grundlage fiir eine etwa spater vorzunelimende 
kritische Revision gegeben. Aus diesem Grunde wurde die Beschrei- 
bung der von Mo. und Janssonius (1) in die Literatur eingefiihrten 
Methode angepaszt, soweit dies angesichts des Erhaltungszustandes 
der fossilen Hélzer eben méglich war. Das soll auch hier geschehen; 
hinsichtlich aller Hinzelheiten kann auf die schon genannten Arbeiten 
verwiesen werden. 

Beschreibung des anatomischen Baues (Topographie): 

Zuwachszonen mit freiem Auge kaum sichtbar, unter dem 
Miskroskop an einer deutlichen Anhaufung und damit verbundenen 
Grészenabnahme der Gefasze kenntlich. Die tangentialen Schichten, die 


10 


auf dem Quersehnitt fiir das blosse Auge Zonengrenzen ahnlich sind, 
enthalten zahlreiche, stets von reichlichem Holzparenchym umgebene 
Harzgange und auch Gefisze, aber fast kein Libriform. Diese 
Schichten nicht iiberall gleich deutlich, stets eine Reihe Harzgéange ent- 
haltend, von denen 2 benachbarte zuweilen verschmelzen (auf 18 mm 
radialer Erstreckung kommen 5 Harzgangreihen, die sich iiber einen 
eroszen Teil des Querschnitts verfolgen lassen). (Textfig. 1, Tafel, 
Fig. 1, 2). Gefasze + gleichmaszig verteilt, za S—16 auf dem mm?, 


ST 0) 
IOO~ (5, OO 


@K@ 


H 
® 
i | 


Fig. 1. Querschnitt. 


in der Regel vereinzelt legend, seltener in Gruppen, dann oft zu 
zweien. Sehr oft an beiden oder wenigstens an einer Seite an Mark- 
strahlen grenzend, sonst meist von Holzparenchym oder Fasertra- 
cheiden umgeben. Diese sehr sparlich, nur an Gefasze grenzend. 
Libriformfasern die Grundmasse des Holzes bildend, + undeut- 
lich in radialen Reihen angeordnet. ; . 

Kinfaches Holzparenchym die Gefaisze und Harzgange 
umgebend, tangentiale Bander bildend, einige zerstreute Fasern anschei- 
nend auch im Libriform eingesprengt; die die Harzgange umgebenden 
Zellen oft in die Breite gezogen, kaum in den Harzgang hineinragend 
(diinnwandiger als die anderen). Harzgange nur in den tangentialen 
Bandern zahlreich, ausserhalb derselben nur vereinzelt. Markstrahlen 
seitlich von einander getrennt durch 1—10 Libriformfaserreihen, 15; 


14 


am haufigsten 3—5-schichtig, 3—30 Zellen hoch, die breiteren 
nicht immer aus 3 Stockwerken zusammengesetzt, das obere und 
untere dann meist eine, seltener bis 4 Zellen hoch, die wie die der 
einfachen Markstrahlen aufrecht oder aufrechten abnlich sind. Die 
breiteren Stockwerke oft von tangential haufig sehr breiten Hiill- 
zellen umgeben. Nicht selten stehen mehrere Markstrahlen, nur 
dureh ein oder zwei Fasern von einander getrennt, itbereinander, ver- 
schmelzen auch gelegentlich ganz (Tafel, Fig. 3; Textfig. 2). Ihre 
Zellen enthalten oft Kristalle. 


Fig. 2. Tangentialschnitt. 


Beschreibung der Elemente: 

Gefisze: Weite radial 65—275 uw, tangential 70—210 u, ellip- 
tische, auch Kreiszylinder, Querwande + horizontal (selten sichtbar), 
Perforation + unkenntlich (lochformig?) mit zahlreichen Hoftiipfeln, 
wo sie aneinander oder an Fasertracheiden grenzen, Tiipfel polygonal- 
rundlich oder elliptisch; die Pori oft elliptisch, schief bis vertikal 
gestellt; mit einseitigen Hoftiipfeln und einfachen Tipfeln, wenn an 
Holzparenchym und Markstrahlen grenzend, haufig mit dinnwan- 
digen Thyllen erfiillt. 

Fasertracheiden: Nur in der Umgebung der Gefasze vorhanden, 
Tiipfelung wie bei den Gefaszen. 

Libriformfasern: Weite radial 85—16 yp, tangential L1O—16 u, 


12 


polygonal mit oft abgerundeten Kanten, oft anch vierseitig. Tiipfel 
spaltenformig, seltener auch rundlich. Interzellularréaume wurden 
nicht beobachtet. 

Holzparenchymzellen: Weite radial 10—35 u, tangential 10— 
30 u, Lange 40—200 uw, 4—8-seitige Prismen mit abgerundeten Kanten 
und vertikaler Achse, die Zellen um die Gefasze und namentlich 
um die Harzginge oft in die Quere gezogen, mit einfachen Tiipfeln, 
wo sie aneinander und an Markstrahlen grenzen, im iibrigen vgl. 
das bei den Gefaszen bzw. dem Libriform gesagte. Die Tiipfel oft 
auf der Radialwand in 1 oder 2 vertikalen Reihen angeordnet. 
Interzellularen nicht erkennbar. 

Harzgange: Weite radial 30—90 uw, tangential 30—80 u, darin 
gelegentlich braune Harztropfen. 

Markstrahlzellen: 

1. Liegende: Weite radial 30—80 yu, tangential 7—20 uw, Lange 
10—40 wu, polygonale Prismen mit radialer Langsachse und abge- 
rundeten Kanten, die tangentiale Wand meist senkrecht stehend, 
getiipfelt wie die Parenchymzellen. 

2. Aufrechte: Weite radial 30—60 yp, tangential LO—20 u, Lange 
20 —60 uw, mit langsgerichteter Achse, im iibrigen wie die liegenden 
Zellen. Inhalt fast stets Harz, auszerdem sehr oft in den aufrechten, 
aber zerstreut auch in Hiillzellen und liegenden Zellen ein deutlicher, 
meist + kleiner Einzelkristall, der in der Regel nur einen Teil des 
Zellinneren ausfiillt (Tafel, Fig. 4, 5). 

Bestimmung des Holzes: 

In der Beschreibung fehlen, gemessen an der ,,Linnean Method” 
von Moni und Janssonius, viele Einzelheiten. Das ist eine Folge der 
zum Teil mangelhaften Erhaltung des Fossils. Dennoch ist eine 
Bestimmung durchaus moglich. Charakteristische Merkmale sind die 
Markstrahlen, das Parenchym und die Harzgange, die erkennen lassen, 
dasz in dem Holz eine Dipterocarpaceenart vorliegt. Solche 
waren auch unter dem Djambimaterial ‘KrAusgt 1) haufig; sie sind 
als Dipterocarpoxylon Tobleri, Dipterocarpoxylon sp. (? Tobleri) und 
Dipterocarpoaylon sp. beschrieben worden. Dazu tritt noch Diptere- 
carpoxrylon burmense Houpex, und es konnte schlieszlich gezeigt 
werden, dasz auch Grewiorylon Swedenborgii Scuuster sowie Wobur- 
nia Scotti Stopes zu Dipterocarpoxylon gestellt werden miissen, von 
denen die erste Art Dipterocarpoxylon Tobleri recht nahe steht, aber 
hohere Markstrahlen und gefachertes Holzparenchym besitzt. 

Sehen wir von Dipterocarpoaylon Scotti aus der unteren Kreide 
Englands ab, das wegen seiner anders verteilten Harzgange und der 
im ubrigen + mangelhaften Erhaltung fiir den Vergleich mit dem 


13 


vorliegenden Fossil nicht in Frage kommt, so sind alle diese Holzer 
auf Siidostasien beschrankt. Mit keinem kann das Holz von Bolang 
vereinigt werden. Dipterocarpoxylon burmense besitzt einreihige 
Markstrahlen, Dipterocarpoxylon sp. viel grészere Gefasze und haufi- 
geres zerstreutes Parenchym, Diplerocarpoxylon Swedenborgi viel 
héhere Markstrahlen (bis 80 Zellen hoch) und teilweise geféichertes 
Parenchym. Dipterocarpoaylon Tobleri schlieszlich stimmt in allge- 
meinen zwar mit unserem Holz gut tiberein, doch ergeben sich fiir 
dieses folgende Unterschiede: Alle Elemente sind relativ viel kleiner, 
das wird yor allem deutlich bei Gefaszen, Harzgaingen, Hohe und 
Breite der Markstrahlen. Wenn auch diese Verhaltnisse innerhalb 
einer Art individuellen Schwankungen ausgesetzt sind, so diirften 
derartige Unterschiede (die Weite der Harzgange z. B. bei Dipterocar- 
poxylon Toblerr 1O0O—300 u, hier nur 30—90 w), wo es sich doch 
unzweitelhaft um altes Stammholz handelt, systematisch bedingt sein, 
Namentlich der Tangentialschnitt mit den verhaltnismaszig viel 
breiteren Markstrahlen bietet ein ganz anderes Bild. Dazu kommt 
in den Markstrahlen das haufige Auftreten von Einzelkristallen, die 
Dipterocarpoxrylon Tobleri ebenso wie anscheinend allen anderen 
bisher beschriebenen Formen durchaus fehlen. Dass es sich hierbei 
nicht um etwaige schlechte Erhaltung handeln kann, ist bereits 
betont worden (Kravser. 1). Das vorliegende Fossil, dessen Gewebe 
viel schlechter erhalten ist als das eines Teiles der Djambihdélzer, 
zeigt aufs Neue, dass gerade die Kristalle, wenn tiberhaupt vorhan- 
den, auch sehr gut erkennbar bleiben. 
Ks ist eine neue Form, die als 


Dipterocarpoxylon javanense 


bezeichnet werden soll. 

Mit einer bestimmten lebenden Art kann das Fossil bei dem 
derzeitigen Stande der anatomischen Holzuntersuchung kaum identi- 
fiziert werden. Es sei auf das an anderer Stelle gesagte (KRAusEL 1) 
verwiesen. Auszuschliessen diirfte die Gatiung Dipterocarpus selbst 
sein, bei der die Markstrahlkristalle nach allen bisherigen Unter- 
suchungen fehlen. Sie finden sich dagegen sicher bei Arten von 
Hopea und Vatica. Auch Moin und Janssonius (1 | 347 u. f.) 
geben sie nur fiir Hopea fagifolia Mig. und Vatica bancana Scuurr. 
an, wo sie aber nur in den aufrechten Markstrahlzellen auftreten. 
Jedoch fehlen beiden Zuwachszonen und Vatica bancana auch die 
tangentialen Harzgangreihen, wozu noch manche kleinere Unter- 
schiede kommen. Nach alledem handelt es sich bei dem Fossil also 
vielleicht um eine Hopea-oder Vatica-art. Gerade die Haufigkeit und 


14 


Verteilung der Harzgange scheint ja ziemlich groszen Schwankungen 
innerhalb der einzelnen Gattungen zu unterliegen. 

Die bisher bekannt gewordenen Dipteroearpoxyla sind tertiaren 
Alters, und dies gilt wohl auch fiir Dipterocarpoxylon javanense. 
KieselhOlzer sind ja im Tertiar des ganzen Gebietes weit verbreitet, 
und sehon Goneprrr (1) hat soleche in seiner Tertiarflora von Java 
abgebildet, ohne dasz allerdings seine Bilder eine Bestimmung der 
Holzer ermoglichen wiirden. 

Immer wieder zeigt sich also, dasz die Dipterocarpaceen auch im 
Tertiir in Siidostasien weit verbreitet waren. Wir gehen daher in 
der Annahme kaum fehl, dasz sie schon damals eine Abnliche Rolle 
wie heute in der Flora des Gebietes gespielt haben, dasz diese also 
verhaltnismasig geringe Verdanderungen vom Tertiar bis zur Jetztzeit 
durehgemacht. hat. 

Zum Schlusse mégen noch die bisher bekannt gewordenen fossilen 
Dipterocarpaceenhédlzer in Form eimer Tabelle zusammengestellt 
werden. 


DIPTEROCARPOXYLON Ho.pen. 


1. a) Markstrahlen ohne Kristalle 2 
b) Markstrahlen mit Kristallen D. javanense 
(Tertiar? Bolang, Java). 
2. a) Markstrahlen mehrreihig 3 
6) Markstrahlen einreihig D. burmense 


(Tertiar, Burma). 
3. a) Harzginge in (+) langen tangen- 
tialen Parenchymbiandern aol 
6b) Harzgainge nur sehr zerstreut D. Scottit 


(untere Kreide, England). 
4. a) Neben den tangentialen Reihen 


auch zerstreute Harzginge : 5 
6) Neben den tangentialen Reihen 
keine zerstreuten Harzgange D. sp. 
(Tertiar, Sumatra). 
5. a) Die tangentialen Harzgangreihen 


sehr lang 6 
6. Die tangentialen Harzgangreihen 
kiirzer, oft unterbrochen D. sp. (Tobleri?) 


(Tertiar, Sumatra). 


S 
& 


) Markstrahlen bis 80 Zellen hoch, 
die Einzelzellen bis 140u hoch 
(gefachertes Parenchym) D. Swedenborgit 
(Tertiair, Ostindien). 
6. Markstrahlen bis 50 Zellen hoch, 
die Einzelzellen bis 90u hoch 
(einfaches Parenchym) D. Toblert 
(Tertiair, Sumatra): 


15 


Die Zahl der bisher untersuchten fossilen Hélzer des Gebietes ist 
angesichts der Haufigkeit ihres Vorkommens verschwindend gering, 
-obwohl sie einen wesentlichen Beitrag zur Kenntnis der fossilen 
Flora liefern wiirden. 


ABBILDUNGEN. 


Textfig. 1. Querschnitt, Uebersichtsbild. 


Tafel, Fig. 1. Desgleichen. Markstrahlen, Gefisze, tangentiale Holzparenchym- 
binder mit Harzgiingen. °5/;. 


. Tafel, Fig. 2. Desgleichen. *5/;. 
Tafel, Fig. 3. Tangentialschnitt. Verteilung der Markstrahlen. 2°/,. 
‘Textfig. 2. Desgleichen. 59/,. 


Tafel, Fig. 4, 5. Radialschnitt. Aufrechte und liegende Markstrahizellen, teilweise 
darin Harz und Kristalle. 15°/,. 


LITERATURVERZEICHNIS. 


Goeprert, H. R. (1), Die Tertiarflora der Insel Java. ’s-Gravenhage 1854. 

Hotpen, R. (1), Fossil Wood from Burma. Rec. Geol. Surv. of India XLVII. 1916. 

Kravset, R. (1), Fossile Hélzer aus dem Tertiir von Siid-Sumatra. No. 4 der 
»Beitrige zur Geologie und Paliontologie von Sumatra; unter Mitwirkung von 
Fachgenossen herausgegeben von Aug. Toxter, Basel”. Verhand. Geol. Mijnbouwk. 
Genootsch. Nederl. en Kol. Geol. Ser. V. 1922. 

Mou, J. W. und Janssonius, H. H. (1), Mikrographie des Holzes der auf Java 
vorkommenden Baumarten |. Leiden. 1906. 
~ Mott, J. W. und Janssonws, H. H (2), The Linnean Method of Describing Ana- 
tomical Structures. Rec. Trav. Bot. Néerl. IX. 1912. 
_ Scuuster, |. (1), Ueber Nicolien und Nicolien dhnliche Hélzer. Kung. Svensk. 
Vetensk. Akad. Hand. XLV. 1910. 

Stopes, M., (1), Petrifactions of the Karliest European Angiosperms. Phil. Transact. 
Roy. Soc. London. B. CCIV. 1913. 


Dezember 1921. Frankfurt a.M., Geologisch-Paliontol. 
Institut d. Universitit. 


Anatomy. — “On the Significance of the Supra-orbital Ridges in 
the Primates.” By Prof. L. Box. 


(Communicated at the meeting of February 25, 1922). 


The significance of any morphological feature may be gathered 
either from the function it performs, or from its mode of origin. 
Of these two methods it is always best to follow the first and to 
employ the second only when the first fails or yields unsatisfactory 
results. That the first method yields more reliable results is sub- 
stantiated by the fact that in the application of this method direct 
observations are the basis for our conclusions, which in the other 
case are supported at best by more or less plausible reasoning and 
speculation about the possible influences and correlation of phenomena. 

What I wish to state about the significance of the supra-orbital 
ridges in the Primates I have preceded by this contrast between the 
two methods of scientific morphological research, since not long ago 
the same subject was raised at one of our meetings by our fellow- 
member Prof. Dusois, who chiefly adopted the second method. I also 
propose to discuss the question of the supra-orbital ridges of the 
Primates — about which I pronounced my opinion on a previous 
occasion. However, in my discourse | will scrupulously keep within 
the bounds of immediate observation. 

First of all let us consider the facts. When comparing the human 
skull with that of Anthropoids -— to which group I will confine 
myself for the time being — we are struck at once by the difference 
in contour where the cerebral crane passes into the facial skull. 
That this difference is accentuated by the orthognathy of the human 
skull as contrasting with the marked prognathy of the Anthropoid 
skull, is only of secondary importance for our problem. The Anthro- 
poid skull has no external frontal vault, which is the reason why 
some consider this skull to be flattened. This belief may be sup- 
ported by the comparison of young Anthropoid skulls with those of 
adults. In the former the supra orbital ridges are absent, which 
makes the skull look much more like that of man. The ridges are 
formed as the ape grows up. This development commences shortly 
after the complete eruption of the milk set about the time when 
the first permanent molar appears. 


17 


Now what is the function of these supra-orbital ridges? To find 
the answer the researcher should ascertain the part played by these 
ridges in the structure of the skull as a whole, and what is their 
topographical relation to their immediate surroundings. This may be 
done quickest by making a sagittal section that extends along the 
axis of the orbit, through the ridge and the adjoining part of the 
skull. The image resulting from it is represented for Gorilla in fig. 1. 


Fig. 1. 


What does this figure teach us? First of all that, properly speaking, 
the term supra orbital ridge is not quite fit aud that this formation 
cannot be compared with the occipital-, and the sagittal ridge also 
characterizing the skull] of Gorilla. For, in reality, of this so-called 
supra-orbital ridge the lateral portions form the roof of the orbits, 
while the central part forms the roof of the nasal cavity. If, there- 
fore, the supra-orbital ridge should be removed, nearly the whole 
content of the orbita would be deprived of the overlying osseous wall 
and would consequently come to lie immediately under the skin. 

Direct observation of the topographical relation, therefore, leaves 
no manner of doubt about the function of the so-called supra-orbital 
ridge, it is namely the indispensable osseous wall of the orbita at the 
top. It is not a crest like the crista sagittalis and the crista 
occipitalis, but it is an indispensable wall of a cavity in the skull. 
But if this is a fact the origin of the superorbital ridge must be 
closely allied to general growth-phenomena of the skull after the 
early childhood of the ape. For we stated that, notwithstanding the 
absence of the supra-orbital ridges in the child-ape, still also here 

2 

Proceedings Royal Acad. Amsterdam. Vol. XXYV. 


18 


the orbita is provided with an osseous roof. It is a fact, indeed, 
that in this part of the skuil radical changes have taken place in 
the topographical relations. These changes may be summarized as 
follows: in the child-anthropoid, and a fortiori in the fetus, the 
orbits are situated under the cranial cavity, whereas in the adult they 
are for the greater part precerebral. While they are lying under the 
cranial cavity the bottom of this cavity makes up the roof for the 
orbits, but when the orbitae are shifted precerebral a new roof 
is to be formed for an adequate protection of the contents. That we 
really have to do here with a displacement of the whole content 
of the orbita anteriorly and not with a simple enlargement of the 
orbitae, is illustrated by Figs 2 and the folllowing. They represent 
casts of the cranial cavity and orbita, in situ. 


Fig. 2. 0 Fig. 8. 

These casts were made in the following way: Copper wire of 
adequate thickness was stuck through the communications between 
orbit and cranial cavity; subsequently the orbit and the cranial 
cavity were filled with plaster of Paris. Finally the enclosing skeleton 
was cautiously removed with a chisel. In this way an exact image 
is obtained of the topographical relations between the cranial cavity 
and the orbita. 


19 


Fig. 2A represents a cast of the cranial cavity and orbita of a 
young Macacus cynomolgus, Fig. 2B those of an adult specimen. 
A dotted line indicates the location of the eye-ball. When comparing 
the two figures, the difference between the young and the adult 
specimen as to topographical relation of the orbita and consequently 
of the eyeball, is quite obvious. In the young specimen the eyeball 
is still subcerebral, in the adult it is on the other hand precerebral. 

The same holds for Siamanga syndactylus, though in a smaller 
degree than for Macacus, as will be seen in Fig. 3A (young animal) 
and 3B (adult). Here the anterior displacement of the orbit during 
growth is not so considerable as with Macacus, which accounts for 


va aN 


20 


the fact that in Gibbon the so-called supra orbital ridge is less 
developed than in Macacus. 

This is the case in a still smaller measure in Orang, as appears 
from a comparison between fig. 4A and 4B. Although we distinetly 
observe here an anterior shifting of the orbita, it is only slight. 
This is why in Orang no supra-orbital ridges have been developed, 
but only a general thickening of the frontal bone immediately over 
the orbitae. 

A comparison of the figures 2, 3,and4 inter se clearly shows the 
causal correlation between the origin of supra-orbital ridges and the 
shifting of the orbitae, for the less this shifting, the less strong the 
ridges will be. 

This appears even more distinctly from a comparison of Fig. 5A 
and Fig. 5B. 


Fig. 5. 


Fig. 5A shows a cast of cranial cavity and orbita of a one-month- 
old child, and Fig. 5B that of an adult man. It will be seen 


R. Krausel: ,,Ueber einen fossilen Baumstamm von Bolang (Java), ein Beitrag zur Kenntnis der 
fossilen Flora Niederlandisch-Indiens.” 


=>. 
é . 
‘ 
x 
- 
ee 
& 
* 
¥ 


Krausel phot. 


Heliotype van Leer, Amsterdam 


Proceedings Royal Acad. Amsterdam Vol. XXV 


21 


that there is no question about a displacement of the orbita, in the 
baby as in the adult the orbita is situated subcerebral, which 
accounts for the complete absence of supra-orbital ridges in man. 

The subcerebral position of the orbitae is a typical feature of the 
human skull, by which it is distinguished from al! other mammalian 
skulls. In this respect the Orang skull is most like that of man. 
Parenthetically I call attention to my former pronouncement, quite 
in harmony with the fact established here: that all typical human 
somatic properties are persisting fetal features. 

The Figures 4A and 4B also induce me to say something relative 
to the so-called flattening of the skull of Anthropoids. The hypothesis 
that the skull of Anthropoids has been flattened through mechanical 
causes, I consider, in principle, erroneous, as it is based only on 
deficient observation and inaccurate measurement. As to the latter 
it must be considered as a fundamental error when, in devermining 
the length-height-index of the skull, the greatest length of the skull 
is considered to be the distance between two points lying on the 
outside of the skull. According to this method the height of the 
skull should be measured from the basion to the superior margin 
of the crista sagittalis. For a comparison of the forms of skulls of 
allied species measures should be used that cannot be influenced by 
a difference in thickness of the cranial bones, or by other adventi- 
tious circumstances. Points on the inside of the skulls should be used. 

But the hypothesis that the Anthropoid skull is flattened, rests on 
deficient observation, as stated above. A flattening of the skull would 
necessarily entail a transformation of the cranial cavity. Now when 
comparing the relative figures it will be seen that in Macacus the 
brains of the adult individual with his large supra-orbital ridges are 
not flatter than those of the young individual, in which the ridges 
were lacking; it will furthermore be seen that the cranial cavity 
of the adult Orang in the frontal region is still as much vaulted as 
in the young specimen. 

The anthropomorphous child has a frontal vault that is visible on 
the outside. The absence of this vaulting in the adult skull is not 
to be ascribed to a flattening, undergone by the frontal region, but 
is due to a shifting of the orbits anteriorly and to their consequent 
precerebral situation. From the vaulted front a new roof overlaps 
the orbita, and the originally apert frontal vault has thereby be- 
come an occult one. 


Mathematics. — ‘Representation of a Bilinear Congruence of 
Twisted Cubics on a Bilinear Congruence of Rays.” By Prof. 
JAN DE VRIEs. 


(Communicated at the meeting of February 25, 1922). 


In a communication entitled: Congruences of Twisted Cubics in 
connection with a Cubic Transformation (these Proceedings Vol. XI, 
p- 84, 1908) I have shown that the congruence of the twisted 
aubics 9* through five points (congruence of Reyz) may be converted 
by a simple transformation (x, yz = 1,4 = 1, 2, 3, 4) into a sheaf of 
rays. Now I shall show how a different congruence [9*| likewise 
by means of a cubic transformation, may be represented on a 
bilinear congruence of rays. 


§ 1. The transformation in question arises in the following way. 
Three crossing straight lines a,, a,, a, are the axes of involutions 
of planes with pairs ag, a’,(k = 1, 2,3); to the point of intersection 
P of the planes a,,a,,«, the point of intersection P’ of the 
corresponding planes a@',, @',, a’, is associated. 

For a point A, of a,,a@, is indefinite; any point of the straight 
line ¢,, which is the line of intersection of the planes a’,,a’, 
corresponding to A,, may be considered as the image of A,. To the 
points of the singular straight line a, the rays of a quadratic scroll 
(t,,;)? having a, and a, as directrices are therefore associated. 

Let ¢ be a transversal of a,,a, and a,, S the point of intersection 
of the three planes «'; associated to the planes a, = taz. Evidently 
S is associated to every point of ¢. The locus of the singular points 
S is a twisted cubic o*, each point of which is represented by a 
ray of the quadratic scroll (¢)* having a,,a, and a, as directrices. 

S being especially associated to the points A,, A,, A, where ¢ 
rests On @,,a,,4,, 6° is the partial intersection of the three scrolls 
(ts2)°, (ts1)’ (t443)7; these have in pairs a straight line a, in common. 

When P describes the straight line 7, the pencils (az) become 
projective; also the pencils (@',) become projective and they produce 
a twisted cubic g? which is the image of the straight line r. As r 


23 


cuts two rays of each of the scrolls (¢,))*, 9° has the straight lines az 
as chords; it rests in two points on o* because r meets two rays t. 
Let us now consider the bilinear congruence of rays {r] which 
has two oft the straight lines ¢ an directrices. Through the cubical 
transformation it is transformed into the congruence [y’] of which 
the curves 9* pass through two fixed points S, and S, and have 
the three fixed straight lines a,,a,, a, as bisecants'). 
' Inversely any congruence [9*] with two base points S,, S, and 
three fixed bisecants az can be represented on a bilinear congruence 
[vr]. With a view to this we take two transversals ¢,, t, of the 
straight lines a, and we define the involution of planes through a, 
by associating the planes (a%S,) and (eS,) to the planes (axt,) and 
(axt,). 


§ 2. The curve 9* degenerates as soon as the ray r resis on one 
of the singular lines o° or ax. 

If 7 passes through the point S of o* its image is composed of 
the straight line ¢ associated to S, and a conic @? through S, and, 
cutting a,,a, and a,. The locus of the conics 9’ is the dimonoid 
of the fourth order, 4‘, which has threefold points in S, and S,, 
contains the straight lines a, and has a double torsal straight line 
ss: 

The image of A‘ is the scroll (r)’ with directrices 9°, ¢, and 4,, 
where ¢, and ¢, are threefold, which has the straight lines a, as 
double generatrices. This- may be verified by combining (7)* with 
a curve m*, which is the image of a straight line a. 

If the ray 7 is to rest on. a,, it must belong to one of the plane 
pencils having the points 6',=a,¢t, or B",=a,t, as vertex and 
belonging to the bilinear congruence of rays (1,1). The former 
plane pencil lies in the plane B’, t,; the image of this plane is the 
scroll (¢,,)? combined with the plane S,a,. For [9°] there is found 
from this a pencil of conies which have S, and the intersections of 
a, and a, with the plane S,a, ase base points. The fourth base 
point is the intersection with the straight line 6',,, which, as a 
transversal through S, of a, and a,, is the image of the point B’,. 
Here we have therefore a group of degenerate figures each consisting 
of the straight line 6',, and a conic of the pencil in question. 


1) This congruence has for the first time been investigated by M. Sruyvaprt 
(Dissertation inaugurale, Gand 1902). A different treatment of the “Congruence of 
Sruyvarrr” is found in the thesis for the doctorate of J. pp Vries, Utrecht 1917, 
where also the literature on bilinear congruences of twisted cubics is mentioned. 


24 


There are of course jive more analogous groups represented by 
the plane pencils having their vertices in B",, B,, B",, B',, B",. 


§ 3. A degeneration into three straight lines is represented by a 
ray of (1,1), which cuts the singular lines twice. This is among 
others the case with the bisecant d of o* which rests on ¢, and ¢, 
(and differs from a,,a@,,a,). Its image consists of the straight line 
d,, =, S, and the two transversals ¢ and ?¢" that rest on d,,, a,, a, 
and a, and that are the images of the points were d rests ono’. 

The image of the ray 6, 5", consists of the line of intersection 
of the planes «', and «', corresponding to the planes «¢,=a, B’, 
and «, =a, B’, and of the straight lines 6',, and 6",,. Through com- 
bination of the points By, and B", we find in this way six configu- 
rations 9? formed by three straight lines. 

The straight line 6',, lies on A‘; together with S, it defines a 
plane; the straight line in this plane through S, intersecting a, 
forms together with 6',, and the straight line ¢ resting on it a con- 
figuration 9°. 

There are apparently five analogous configurations ; the congruence 
[v’] contains accordingly in all thirteen of those figures, each con- 
sisting of three straight lines. 


§ 4. The curves of |g*| resting on a straight line /, are repre- 
sented by the straight lines 7 of the (1,1), which cut a curve A° 
that has a,, a,, a, as chords and that meets o* twice. These straight 
lines + form a scroll of the sixth order, (7)°, with threefold direc- 
trices ¢,,¢, and double generatrices az. The straight line 7, which 
is a chord of 4°, hence a double generatrix of (r)*, bas for image 
a curve o,° that ineets / twice and which is therefore a double 
curve of the image of (r)’. As therefore an arbitrary straight line is 
cut twice by only one e*, |9*] is a bilinear congruence. 

The image p* of a straight line m has four points on a, in common 
with (7)’, for this curve cuts the double straight line a, in two points. 
Besides the straight lines az m* and (r)" have six more points in 
common; hence the image of (7) is a surface of the sixth order, 
A’, with three double lines, az, and the double curve @,°. 

If w* passes through a point of the line ¢, (which is threefold on 
(r)’, m contains only three points of A® outside the singular lines; 
here S, and S, are therefore threefold points. 

On A® there lie also the six lines 6 (§ 2) as component parts of 
the degenerate figures of which the conics 9? rest on J. 


25 


§ 5. The transformation used here, gives also the representation 
of another congruence {o*|. Let us consider the image of the sheaf 
that has M’ for centre. A ray 7" through JM’ cuts each of the scrolls 
(@) and (¢,)? twice and is therefore the image of a curve 9? through 
the fixed point J/ that cuts 6° and the lines a, twice. This [g’] is 
a special case of a congruence described by VENnrERont ‘). 

Through a point there passes one 9* of this congruence. A curve 
w, the image of a straight line 77, sends one chord through M’; 
hence m is a chord of one curve g’. Also this [e*| is therefore 
bilinear. 

If 7’ intersects the curve 6’, y* consists of a straight line ¢ anda 
oe’ through J, which intersects 6° twice and which rests on a,, a,, 
a, and ¢t. The cone 4* projecting 6° out of JM’, has two points of 
6 in common with a uw’; there are accordingly seven o* resting 
on m. The conics of the degenerate figures in question form there- 
fore a surface yw’; on this a,,a,,a, are double lines (each straight 
line ¢ defines one point S, hence one ray MW’S, and cuts w’ for this 
reason besides in az in one more point) and o°® is a threefold curve 
(¢ meets three generatrices of 4°). 

The surface wy’ is represented on a plane by the chords of o°; 
it is therefore a rational surface and belongs to the group of homa- 
loids to which I have drawn attention in a communication of 
Vol. XX, p. 419 of these Proceedings. 

If 7’ rests on a,, 9’ degenerates into a straight line ¢,, (the image 


of the point a,7') and a 9’ of the plane @ corresponding to the 


plane a'= M’a,. The conics 0’ form a pencil with base points J/, 
the points A, and A, of a, and a,, and the intersection of « with 
o°, which point does not lie on a,. Each 0? is connected with a 
straight Jine ¢,, and this rests on a,,a, and o°. 

There are accordingly in all four systems of compound figures Q°. 

The chord of o* passing through M7’, is the image of a @* com- 
posed of two straight lines ¢ and the straight line through J/ which 
cuts them and which is at the same time a chord of o°. 

The transversal of a, and a, through JM’ is the image of a 9° 
formed by a straight line ¢,,, a straight line ¢,, and their transversal 
through M which rests at the same time on a, and a,. 

The transversal through J/’ of a, and o° is the image of a 9° 
formed by a straight line ¢, a straight line ¢,, and their transversal 
through M which rests at the same time on a, and on o°. 

There are therefore in all seven figures 0° consisting of three 
straight lines. 


1) Rend. Palermo XVI, 209. 


26 


The curves 9° resting on a straight line /, are represented by the 
generatrices of the cone that projects the curve 2° out of M’. As 
this cone is cut by a w* in nine points, the curves @* intersected 
by / form a surface 7’. On this surface a,,a,,a, and 6° are three- 
fold lines, because any straight line ¢,, and any line ¢ cuts the 
cone (M’, 23) three times and the image of the double generatrix of 
this cone is a double curve of 4’. Any curve of [9*} has 8x3 
points in common with A’ on the singular lines; hence M is a 
triple point of 4’. 


Physics. — “Research by means of Réintgen-Rays on the Structure 
of the Crystals of Lithium and some of its Compounds with 
Light Elements. UW. Lithiwn-Hydride’. By J. M. Buyorr and 
A. Karssen. (Communicated by Prof. P. Zeeman). 


(Communicated at the meeting of February 25, 1922.) 


1. Introduction. The investigation with X-rays on the structure 
of lithium-hydride was taken up in connection with the analogy 
drawn by Moegrs') between lithium hydride and the heteropolar 
alkali halogenides. 


2. Réntgenograms. The photographs were made as described in 
our preceding paper’). The difficulty presented itself that after the 
exposures the hydride-content had been reduced by 15 or 20 percents 
of weight. The parasitical lines were eliminated: by comparing 
the photographs of samples of decreasing hydride-content (the place 
of the LiH-lines appeared to be independent of the degree of decay, 
hence no formation of mixed crystals); by photographing a coarse 
crystallized, non-rotated sample, appeariug the interference lines of 
LiH markedly distinguished by dots of greater intensity; by 
checking up the parasitical lines by those of LiOH). 


3. Calculation. The table contains for LiH the values of 10° 
cy : 
sin? 3 for the centres of the a-lines. As appears from the occurrence 


of a factor 77,5 + 0,5 LiH is regular, and the side of the elementary 
cell a=4, 10.10-8 ecm. From this common factor the number 
of particles per elementary cell, m is calculated to be 4.30, with the 
aid of the density according to Morrs, mol.weight, constant of AvoGapRo, 
and wavelength Crx, (resp. 0,816 ; 7,94; 0,6062 . 10** and 2,284 .10-). 
This points to n= 4, which is in agreement with the supposed 
NaCl structure together with the absence of the planes of mixed indices. 


1) Morns, Z. f. allg. u. anorg. Chem. 113, 179, (1920). 
Nernst, Z. f. Elektrochemie 26, 323 and 493 (1920). 
2) Buvoet and Karssen. These Proceedings Vol. XAIII, p. 1365. 


28 


Putting n—4 the said common factor determines the density at 
0,76 + 0,01"). In absence of all further erystallographical data we 
have confined ourselves to the question whether sticking to a NaCl 
or ZnS structure an electron grouping could be found, according to 
the intensities of the reflections found. 

The table gives the observed and calculated intensities. Only those 
factors which bring about an abrupt change in the intensity as 
function of 2/7, have been taken into account, viz. the factor of 
the number of planes and the structure factor, in which the influ- 
ence of the configuration of the electrons too has been accounted 
for. For this were tested some approximative suppositions. We have 
considered the possibility that the valency-electron remains near its 
mother-nucleus (atomic lattice); that the Li has lost its valency- 
electron to the hydrogen (ion lattice)*); that binding of Li and H 
takes place by means of rings of electrons revolving round the 
connecting line in planes normal to the non intersecting trigonal 
axes halfway the Li and H nuclei (binding cireles; passing along a 
trigonal axis two-electron-rings may be imagined between Li and 
H: molecular lattice, case A; or one-electron-rings between Li and 
H as well as between H and Li, case B). 

As to the orbits of the electrons it has been assumed: 1. that the 
electrons are so near to their nucleus that they may be supposed 
to lie in one point (points; reflecting power proportional to the 
number of electrons); 2. that the connecting line of nucleus and 
electron is of a definite length vy, and is equally occuring in all 
orientations throughout the part of the crystal that is cooperating 
in the interference (spheres; diminishing factor for such an electron 


PS pH 
sir 2a = 
a 
Se! in which H=\y2h?"*)); and 3. that these connecting 
oO 
a 
a 


lines are in planes normal to the non-intersecting trigonal axes, 
all the directions equally occurring in those planes (rings: diminish- 


off . : 
ing factor J, | 2%——siny }, in which J, 


» is the Bessilian-function of 
a 


the order of magnitude 0 and y the angle between orbit and lattice 
plane‘). In the binding cireles also only circular orbits have been 


') Impririties have no influence on this value of the densty, as there is no 
formation of mixed crystals. 

2) Also the less probable case Li-H+ has been considered. 

3) Cf. Korxmeyer, These Proc. Vol. XXIII N°. 1, p. 120. 

4) Cf. Coster, These Proc. Vol. XXII N°. 6, p. 536. 


29 


e off = Suu-_ 


« 


ae 0) 
a cc‘0 a 


Bull-_Y 
3uul- YY 


“goo = IT Suls s0jno0 


« 
«“ 


B coo = Buy 1 snipey Vic O a Sa staunt Snipe 
sty} uy (¢ eZ0=4 (S161) 06% ‘92 [IA] “SPW ‘1d ‘YHOg 0} Sulpsoooe siyy uy () 
Pr cel |S 7c Stel cz | 9¢ | 61 LI Ie (eA Al ZS a 10 821 8Z1 s zz | $€6| § 
OL 96 | zol| 29 IL | #9 | 66 | #9 | OL | Sc | #6 | OF2| ZéI 96 0 SZ m&| ¢c8| F 
ce 6: |) 68) |e LS) ge) | Hee |) (See os) lob) 9c) || 9674" eles cel 261 261 sui oz | 919] € 
0g 9! ol 81 6 os | se | si 8 Wei) Oe | Fe |) o) 96 96 sui ooz | zig] 2 
Ol (63) es fi Wer de || Cie MCA Sh os | +9 ze 0 z IDOE \ Ata 
a dq Vv B I ‘8 st 2B ‘I 2 aL e 4 *su0}e *suOL fe 5 
=a & Uv & 
= > x 
“I}S-|DBN | “49S-1DEN “4yS-SUZ “1]S-[DBN “YS-SuZ *1)S-[DBN *1]S-SUZ *4S-[DBN 3 5 Boule 
eee = 3 
= = = 3 
F et 2. s ® 
(c ‘s8uly ae (, sdury ‘(, sesayds *SJUl0d g 9 8 a 
=z =. wi s 
oO a 
wn a 


‘SOI}ISUBJU] payejnojeD 


30 


considered, and here too relation of phases has been neglected 
(diminishing factor as under 8). *) 

The influence of the heat motion, of which nothing is known 
for the different electrons, was left out of consideration. The radius 
of the comparatively small inner ring of Li has always been taken 
equal to Bour’s initial value’); in all the suppositions mentioned 
it has been examined what values of the radii of the other orbits 
made the caleulated and observed intensity concordant. Finally the 
supposition “rings, e4— = + 5/6 times the radius of a two-quanta 
ring in a free H -ion” appeared to give the best agreement. As a 
specimen some of the calculated intensifies are given i.a. those for 
Bonr’s initial values of g, and in the last column the case 
vy — = + 0,6a and gy pi+ = + 0,05a, which is in agreement with 
the observations. 

In how far the factors neglected here, as heat motion, and the 
occurrence of non-circular orbits, may affect the conclusions drawn 
here, must at present be left undecided. 


4. Summary. The Réntgenogram of lithium hydride (method 
Depyrk-ScHERRER) has been taken with Ke, rays. LiH appears to 
crystallize regularly with 4 LiH per elementary cell. [Side a= 
4.10.10-8 em.]. The density is found to be 0,76 + 0,01., On the 
basis taken for the calculation the following assumptions appeared 
to be most satisfactory: NaCl-structure with positive Li-ions and 
negative H-ions; systems of two-electron rings both round Li- and 
H-nuelei with radii resp. + 0,05a and + 0,6a, the planes of which 
are normal to non-intersecting trigonal axes. 

In conclusion we express our great indebtedness to Prof. Smits 
for his valuable help and the great interest he took in our work. 


Laboratory of Physical and Inorganic Chemistry. 
Amsterdam, February 15, 1922. 
1) In Cosrer’s computation of the binding circles of diamond this has also been 
introduced, whereas KoLKMEYER bases his calculations on an undisturbed phase 


relation. 
2) Bour, Phil. Mag. (VI) 26 490 (1913). 


Bacteriology. — ‘Studies about p’Hereiie’s Lacteriophagus’. By 
J. W. Janzen and L. K. Woxrrr. (Communicated by Prof. 
C. Eykman). 


(Communicated at the meeting of February 25, 1922). 
I. The Bacteriophagus in Enteric Fever. 


We have succeeded in proving the existence of this bacteriophagus 
in the faeces of patients recovering from enteric fever, as has also 
been described by pb’ Herete. 

If pb Here.ie’s views are right, it must be possible to influence 

the process of enteric fever favourably by administering bacterio- 
phagum antityphoideum. 
_ We have tried this in three cases and perhaps we have observed 
a somewhat favourable result, but not a striking success. The 
explanation hereof might be found in the fact that this bacterio- 
phagus did not happen to be adjusted at the bacterium, that caused 
the illness of these patients. We have considered it worth while to 
examine this systematically. 

We have been able to make use of three bacteriophagus specimen, 
two of which were from the faeces of patients recovering from 
enteric fever, the third from the faeces of a healthy person who 
had had enteric fever forty years ago. We have examined the effect 
of the bacteriophagi as opposed to 17 typhoid strains, 15 of which 
came from the collection of the Laboratory for Hygiene, the two 
others from the blood of patients out of which the bacteriophagus 
had also been taken. We have steadily examined the clearing up 
of the broth, which has turned slightly turbid by typhoid bacilli 6 
hours old from agarcultures, the checking of the growth of typhus- 
bacilli in broth, and finally the formation of little islands on the 
agarplate(plages). 

What can be the cause of this difference in behaviour? 

It might be supposed that the uninfluenced typhoid strains would 
be so called resistent strains. 

This would be possible for some strains that are not influenced 
by any of the three bacteriophagus strains (3, 8, 20). 

But we also see that the bacteriumstrain which is influenced by 
one bacteriophagus is not influenced by the other, and vice versa. 


32 


TABLE. 


1. Clearing up of the typhoid bacilli distributed in the broth. 

2. Checking of the growth of typhoidbacilli. 

3. Formation of little islands on the agarplate, on which some of the contents 
out of tube I has been smeared. 


Bacteriophagus Wi. Bacteriophagus Sm. Bacteriophagus Re. 


typhoidstrain 1 2 3 1 2 3 1 2 | 3 
Sm. tft] | tt | Ht] — + |++++ 
Wi, |++++)+4++4+|/+++4+] + - - - -- ~ 
~ = ~ — | He [H+] — | ee [Ht 
3 = = see = Es = eat uz 2s 
8 — a — a au = = a* a2 
9 f+tt+] +444) +4] — | t+ ttt] to] 44 [4 
15 r + |++++] - — |+t++] - | +4 [444+ 
19 ~ + J4++++] - — [+444] - — |4++++ 
20 = = = = = = == = = 
23 $e] | EE EEE — = — 
24 — | +4 |++++] - - - -- — - 
25 +44+]4+44+4+]+t++] -— | +44] 4+ J — | 44+ J4+44++ 
20 Jt [tet] tte] Hf HE EH 
21 ~ + |+t+++] — ~ — - = — 
29 = [ASHE EEE = _ - = — = 
31 _ + |ttt++] + | ++ ftt++] — [44+44+]++++ 
82H EES Se as 


Bacteriophagus Wi negative with regard to 1, 3, 8, 20 
4 Sm ¥ 35 1) liso WW, 3518) OR aie ea 
2 Re ” »? ” ” Wi, 3, 8, 20, 23, 24, 27, 29. 


sij agglutination with a highly agglutinating horsesernm (Saxonian 
serum-works) no difference between the strains could be demonstrated, 
they all agglutinated to */,,,,,- 

So it will be necessary to find or to prepare a bacteriophagus 
which also affects the negative strains. 

For the time being we have not succeeded in vitro to adapt the 
bacteriophagus to these. So we shall have to wait until a new 


33 


bacteriophagus is found which fills up this gap, if need be we can 
then administer a mixture of the various bacteriophagi. 

We have been able to convince ourselves that, with a dose of 10 
cM. bacteriophagus per os, the bacteriophagus was already to be 
found the next day in the faeces of two typhoid patients who had 
not had it before. 

D’HERELLE has proved that the bacteriophagus is not absorbed by 
foreign bacilli on which it has no effect. 

Our bacteriophagus however was absorbed by living typhusbacilli 
who were not influenced in their growth by our bacteriophagus. 


February 1922. Amsterdam, Lab. for Hygiene of the 
University. 


Proceedings Royal Acad. Amsterdam. Vol. X XV. 


Bio-Chemistry. — “Lwperiments on Anaphylaxis with Azoprotems’’. 
By K. Lanpsremer. (Communicated by Prof. C. H. H. Sproncx.) 


(Communicated at the meeting of January 28, 1922). 


In previous articles the writer described methods for producing 
immune sera, acting upon known chemical groups. These methods 
are based upon the use of antigens, consisting of proteins, which 
are chemically combined with substances of simple constitution. *) 

As already indicated, the question suggests itself as to whether 
anaphylaxis can be produced by these compounds and what is 
the action in anaphylaxis (sensitization and shock) and antiana- 
phylaxis of each of the two components of the antigen, viz. the 
proteins and the simple substances combined with it. The significance 
of these problerns for the theories of immunity and anaphylaxis and 
the knowledge of the condition of hypersensibility produced by 
simple substances is evident (cf. Dorrr) *). 

The experiments presented here*) form part of a series, the car- 
rying out of which has been delayed because of external circum- 
stances. 

The guinea pigs were sensitized by means of azoprotein *) prepared 
from horse serum and p-arsanilie acid (1 gr. of atoxyl for 100 ec. 
of serum). 

For the second injection an azoprotein formed by combining fowl 
serum and p-arsanilic acid was employed. The use of a number of 
other azoproteins was rendered difficult because of their toxicity 
when injected intravenously. 

Results: lt was found to be more difficult to produce the ana- 
phylactic state with the substances mentioned above than with the 
proteins usually employed, and in the experiments to be described 
it was necessary to make three intraperitoneal injections, correspond- 


ing to 0.5 to 1.0 ce. of serum each, in order to produce consider- 
able effects. 


') Zeitschr. f. Immun. 26, p. 258 (1917), Biochem. Zeitschr. 86, p. 343 (1918). 
2) Doerr, Schweiz, med. Wochenschr. 1921. No. 41. 

5) Details will be given later. 

4) 1. c. Bioch. Zeitschr. 86, p. 359. 


35 


In the case of 14 of the sensitized guinea pigs, the reinjection 
was made intravenously, using 1 to 2 ce. of azoprotein') per 
500 gram weight of the animals. 5 animals died within a few 
minutes, 3 showed severe, 5 slight manifestations of anaphylactic 
shock. Nine control animals showed no symptoms. 

Five animals treated in the manner described showed no ana- 
phylactie reaction after the intravenous injection of azo-compounds 
obtained by combination. of tyrosin and_p-arsanilic acid ; the injection 
of azoprotein (fowl serum + p-arsanilic acid) made an hour later 
failed to produce shock. As a control experiment, in 3 animals an 
azo-compound of metanilic acid and tyrosin was used for the intra- 
venous injection. These animals showed anaphylactic symptoms on the 
subsequent injection of azoprotein (fowl serum + p-arsanilic acid). 

The results obtained demonstrate that guinea pigs previously 
injected with an azoprotein (horse serum ++ arsanilic acid), show 
anapbylactie reactions upon being reinjected with another azoprotein 
containing the same group, i.e. fowl serum + arsanilic acid; but 
they do not show such symptoms upon being reinjected with a 
compound of arsanilic acid and a substance of simple composition, 
i.e. tyrosin. The latter substance, on the other hand, seems capable 
of desensitizing the animals. 


~The Hague. Laboratory of the “R. K. Ziekenhuis”. 


‘) Prepared as indicated in Biochem. Zeitschr. 86, p. 362. 


3* 


Physiology. — “On the Causes of the Emigration of Leukocytes” *) 
By K. J. Ferinca. (Communicated by Prof. H. J. HamBuresr.) 


(Communicated at the meeting of February 25, 1922). 


Dr Haan?) has suggested a method by which in a simple manner, 
without injuring the laboratory animal, large quantities of poly- 
nuclear leukocytes can repeatedly be obtained. He injected into the 
abdomen of his animals fluids such as a starch-solution in NaCl 0.9, 
and other harmless fluids and thereby obtained invariably a homo- 
geneous emigration of polynuclear leukocytes. 

My own investigations were performed systematically aceording 
to this method, with a number of liquids in order to demonstrate 
a definite chemical cause for the emigration of the leukocytes. 1 
experimented on rabbits. 

For shortness sake I will only summarize the results of these 
experiments. 

Whatever liquids were injected (electrolytes, non-electrolytes, more 
or less physiological fluids such as RineGEr’s solution, ultra filtrate 
of serum, sterile serum, olive-oil or paraffin) the result was invariably 
an exudation with emigration of many leukocytes. The process of 
this emigration was the same in all cases. rom this 1 concluded 
that the emigration is not brought on by a specijically chemotactic 
influence exercised by definite substances upon the leukocytes. 

However, there was still a factor that had been left out of con- 
sideration, viz. the concentration of the hydrogen-ions, which recent 
inquiries have proved to play a prominent part in different mani- 
festations of life. 

I considered it rather interesting to ascertain the proceeding of 
the H-ion concentration in the injected liquid at various intervals 
after the injection. 

We used for this purpose the colorimetric method and applied 
phenol-red and cresol-red, recommended by Crark an Loss’). 

Determinations were made in serum of venous blood and in normal 

1) A more detailed communication will appear elsewhere. 

2) J. pe Haay, i.a. Thesis. Groningen 1920. 

3) CLarK and Luss, Journ. of bact. 2. 1. 109, 191 (1917). 


37 


abdominal transudate; the pH of serum was slightly less than 7,6 
and that of normal abdominal transudate 7,6. 

When fluids were injected into the abdominal cavity, a pH of 
7,2 invariably occurred in the exudation after a short time (+ */, 
hour), no matter whether the injected fluid was acid or alkaline 
beforehand. This was the same for all injected substances, also for 
strongly buffered fluids, such as serum. Only the interval before a 
pH of 7,2 is reached, is somewhat longer. This also applied to oil 
and paraffin-injections, the centrifugalized fluid then presented a 
pH of 7,2. 

It appears, then, that a difference of pH from 0,3 to 0,4 exists 
between the blood ana the exudation. At the same time it appeared 
that emigration of polynuclear leukocytes results from the injection 
of the same fluids. 

There is now every reason for correlating the constant occurrence 
of emigration with this constant phenomenon of the changed pH, 
which also always manifests itself, however different the injected fluids 
may be. 

The question may be asked: in how far this differing H-ion con- 
centration may be answerable for the emigration. | have endeavoured 
to solve this problem by maintaining artificially in the injected fluid 
a pH of 7,6 or a little higher, through the addition of alkali, and 
comparing the result obtained with a control-animal, in which the 
injected fluid was left to itself. 1 found from three such experiments 
that in the first case no emigration of polynuclear leukocytes ensued, 
which, however, revealed itself with the control-animal. 

It is evident from these experiments that the degree of acidity is, 
indeed, the causative factor of the emigration of the polynuclear 
leukocytes; it being the only factor which bas altered in the experi- 
ments mentioned. 

We now have to go into the question in what manner this esta- 
blished difference in H-ion concentration with the blood can bring 
about the emigration. Presumable potential differences between fluids 
with various H-ion concentration are the first to suggest themselves ; 
such potential difference might well effect a movement of cells in 
one direction, in casu an emigration. | am analogously reminded 
here of the well-known cataphoretical phenomena found i.a. by HBER 
and his pupils especially in red blood-corpuscles. 

1 thought it desirable by following the example of Hésrr to 
perform catapboretic experiments with red bloodcorpuscles, with 
polynuclear leukocytes and with mononuclear leukoeytes of the 
rabbit in order to ascertain whether they behaved differently towards 


38 


the galvanic current. This appeared, not to be the case: all of them 
moved towards the anode, their charge was consequently negative. 
Through the addition of acid we managed to change their charges: 
when the pH was made less than 4.8, they moved towards the 
cathode. 

In the body, where pH is always greater than 4.8, they will 
always be moved by the current towards the anode. This, then, 
does not afford an explanation of the various behaviour of the 
different kinds of blood-corpuscles in the case of exudation. However, 
we need not, on that account, exclude the possibility of the exndation 
of the polynuclear leukocytes being caused by a potential difference, 
as besides a potential difference other factors come into play, whieh 
may cause or prevent emigration, i.a. the surface-properties with 
regard to the capillary wall, and the ameboid mobility. Hence the 
passive cataphoresis becomes complicated on account of these surface- 
actions. These actions will vary the effect of the cataphoresis in 
different cells in accordance with their composition; even in the 
absence of emigration, the cataphoretic effect even on red blood- 
corpuscles will reveal itself in the considerable accumulation of 
blood-elements in the. abdominal vessels. 

Now I have tried to demonstrate potential differences between 
two fluids differing only in the H-ion concentration. To this end we 
made use of a so-called “dlkette’. 1 sueceeded in demonstrating with 
benzaldehyd and benzylalcohol as oilphase, potential differences between 
fluids with a pH of 7.2 and 7.6. When adding lecithin or a mixture 
of lecithin and cholesterol to the oilphase, the potential difference 
was considerably greater. An addition of cholesterol alone, however 
caused the potential difference to disappear altogether. 

These experiments have proved it to be very probable, that through 
the difference in pH there is also a difference in potential between 
the circulating blood and the exudation. Preliminary experiments 
justified the same conclusion. 

With non-polarisable electrodes we found that under normal con- 
ditions the blood is positive (however slightly) relative to the abdomen, 
while after the injection of a flaid into the abdomen, a reverse 
potential difference manifests itself. These experiments, however, 
will have to be prosecuted further. 

Since we have seen that the bloodcorpuscles may be moved by 
electromotive forces, we are justified in assuming that under the 
influence of the difference in acidity between the blood and the 
exudation, which causes a potential difference, the polynuclear 
leukocytes are moved towards the exudation. The anomalous be- 


39 


haviour of the lymphocytes and especially the red blood-corpuseles, 
may, as stated above, be ascribed to other surface properties of 
these cells. 

In conclusion we may state, therefore, that through injection of 
any fluid whatever, an increased prolonged acidity can be demonstrated 
at the place of injection, which may reasonably be assumed to give 
a certain direction to the ameboid movements of the leukocytes, which 
reveals itself in the constant occurrence of the emigration of the 
polynuclear leukocytes. 

I may still add that in no case does the increased acidity exist 
longer than 18 hours, after the injection of aqueous fluids, but that 
it persists longer after oil injections; this is the reason why with oil 
the emigration lasts longer, as is borne out by all phenomena, i.a. 
the changes in the blood-formula, which cannot be gone into any 
further here. Neither can I expatiate here on the cause to which 
the increased acid formation itself is due. I can state only that there 
is no excessive accumulation of carbonic acid. The only factor we 
can take into consideration is a diminution of the normal reserve 
of alkali under the influence of the formation of acids other than 
earbonic acid. 


Now it is of vital importance to know whether our conclusions 
regarding the emigration of leukocytes in sterile abscesses and 
exudations, also apply in general to every migration of leukocytes 
through the body, e.g. to the emigration of leukocytes in exudations 
of bacterial origin and to the emigration (normal and pathological) 
of the white bloodcorpuscles from the bone-marrow in the blood- 
circulation. Concerning the latter we are inclined to believe that 
normal supply of the polynuclear cells in the blood from the bone- 
marrow is also procured under the influence of a potential difference 
between bone-marrow and blood. It may also be possible that, when 
that supply from the bone-marrow proceeds abnormally, as in cases 
of leukemia, the relation between the pH in the blood and _ the 
bone-marrow is altered. It also avails to know the reason why, in 
the case of fatal infections, the bone-marrow does not react on the 
stimulus of inflammation, why no leukocytes are transmitted to the 
nidus of the inflammation. 

It may be also that without a potential difference between bone- 
marrow and blood or between blood and the nidus of inflammation, 
the emigration of leukocytes is impossible. It should at the same 
time be ‘noted, whether the distribution of lecithin and cholesterol 
in the body may have influence on the generation of electric currents ; 


. 


40 


the significance of a proper relation of these substances for various 
functions of the body, has latterly been pointed out by several 
authors'). Furthermore we have also seen, that cholesterol, added 
to an intermediate phase between two fluids with different H-ion 
concentration, brought about an isolation which prevented an electric 
current. Such an insulator might, therefore, likewise prevent the 
occurrence of an electric current in the body. 


Thus far | have been able to ascertain whether acidity plays a réle only with 
regard to the abscesses in acute inflammation processes In analogy to what we 
have seen in the sterile exudations, it may be expected that in pus or exudations 
of inflammatory nature, in which polynuclear leukocytes predominate, there will 
be a pH considerably smaller than that of the circulating blood. If only mononuclear 
leukocytes occur in the exudations or in the pus, the pH will differ little or not 
at all from that of the blood or the blood serum. It may be presumed, therefore, 
that in acute suppuration-processes there is in the pus a much lower pH than 
that in the serum. In chronic cases of suppuration, especially when there are no 
polynuclear leukocytes, the difference in pH with the blood must be much smaller. 
Likewise in tuberculous pus, where only mononuclear leukocytes occur, we cannot 
expect a great difference in pH with the bloodserum. 

The pH of human bloodserum was determined again by the colorimetric method. 
Here we met with great obstacles in the yellow colour, which is most often peculiar 
to serum and in the occasional excess of fat. In accordance with the values 
established by Evans?) with indicators, we found also in the human serum a 
pH of +7.6. 

Pus from an acute pleuraempyema was examined. The liquid centrifugalized 
from the pus, had a pH of 6.9. The ill-smelling pus contained many streptococci 
and beyond mononuclear- many polynuclear leukocytes and remains of them. 

Pus from a chronic molar abscess with acute exacerbation had a pH of 7, 
beyond mononuclear leukocytes also many polynuclear leukocytes and remains of 
them occurred in the pus. 

In a case of streptococci-meningites the cerebrospinal fluid had a pH of 7.3 
and contained rather many leukocytes, of which 60'/) were mononuclear and 40 °/, 
polynuclear. The next day another puncture was made, and the fluid derived from 
it, proved to be much more cloudy; the pH was then rather more than 7.2. The 
relative number of the various kinds of leucocytes had changed now, the mono- 
nuclear cells fetching only 5°/) and the polynuclear as much as 95°/p. 


lt appears, then, that in these investigations the pH found, agrees 
with the presence of polynuclear leukocytes in the pus or in the 
exudation. 


SUMMARY. 


1. To bring about the emigration of leukocytes from the blood- 


1) Cf. ca. BrINKMAN and vAN Dam, Studien zur Biochemie des Phosphatide und 
Sterine 1—3. Biochem. Zeitschr. bnd. 108, H. 1/3 1920. 
2) C. Lovarr Evans, The Journ. of Physiol. 54, p. 167 and 353. 


41 


circulation, chemotactic properties of definite substances do not come 
into play. The process of the emigration is the same, whatever may 
be the nature of the substances injected for the purpose of obtaining 
the exudation in the abdominal cavity. Neither can any special 
significance be attached to fat and lipoids. 

2. As for the chemical composition of the obiained exudation, it 
appeared that in a short time it becomes about the same as that of 
the normal tissue-fluid. 

3. The injected fluid very soon reaches a higher degree of acidity 
relative to the blood and the normal tissue fluid; independent of its 
being acid or alkaline when injected, a concentration of hydrogen 
ions of about pH 7,2 is produced, while the normal reaction of 
blood and tissue-fluid is 7,6. 

4. This higher acidity must be considered to be answerable for 
the emigration, since the emigration stays away, when the acid re- 
action is checked. 

5. In keeping with this fact also in inflammatory-abscesses, the 
reaction of the fluid relative to the blood is distinctly more acid. 

6. It is possible to consider the emigration as resulting from the 
potential difference arising under the influence of the difference in 
concentration of H-ions between the blood and the injected fluid, 
in the sense of a cataphoretic action. 

7. We call attention to the possibility, that also in other abnormal 
accumulations of leukocytes in the body, as in leukemia, corre- 
sponding factors play a part. 


February 23, 1922. 


From the Phystological Laboratory of the 
Groningen State- Univ. 


Geology. — ‘Observations on the Incandescent Sand Flow of the 
Valley of ten thousand smokes.’ By Rosert F. Grices. 
(Columbus, Ohio, U.S.A.) 


(Communicated at the meeting of April 29, 1922). 


Of the work done by the last expedition (1919) Dr. Escuer has 
seen only the popular account in the National Geographic Magazine, 
September, 1921, Vol. 40 pp. 219--292. This account, written for 
the 725,000 members of the National Geographic Society, was mani- 
festly not the proper place for a technical presentation of the detailed 
data which the geologist requires as the basis for his conclusions. 

A more technical, though only preliminary, account giving more 
geological information has been pnblished by Dr. C. N. Frnner, 
Petrologist of the cooperating party sent with the expedition by the 
Geophysical Laboratory of the Carnegie Institution, in the Journal 
of Geology, Vol. 28, pp. 569—606, 1920, under the title “The 
Katmai Region, Alaska, and the Great Eruption of 1912.” 

A further contribution by E.T. Atiun, Chemist of the Geophysical 
party, dealing not directly with the Incandescent Sand Flow but 
with the ‘Chemical Aspects of Volcanism”, appeared in the Journal 
of the Franklin Institute, Vol. 193, pp. 29—80, January, 1922. 

Further papers giving the scientific results of the Katmai expedi- 
tions in more detail are soon to appear.in the projected Memoirs 
of the National Geographic Society. 


Dr. Escner believes that the hot sand flow was made possible by the 
water of a crater lake which ‘must have” occupied the top of the 
mountain prior to the Eruption of 1912. He is in fact so sure of 
such a lake that he even figures it on his diagram. 

The first and most obvious fact which renders this explanation 
impossible is that Katmai possessed no crater lake prior to the 
eruption. On page 43 is reproduced a section of the United States 
Coast and Geodetic Survey Chart N°. 8555 showing the condition of 
Katmai before the great eruption. It was a three-peaked mass without 
any large crater, essentially similar to its near neighbor Mageik, see 
map on page 45 also a photograph reproduced in the National 
Geographic Magazine, Vol. 31, p. 30, 1917. Both were rounded 
domes built up by repeated flows of viscous lava without admixture 
of cinders or other fragmental products such as appear in the typical 
composite cone, 


43 


Up till the last eruption the ejecta had consisted entirely of basic- 
andesite which had poured out without any explosive accompani- 
ments of a major sort. Between the last of these flows and the 


Katmai volcano before the eruption 


S KILOMETERS 


3 MILES 


Faas \\ 
y, 17500 | Vii Si) 
‘--" KATMAI Vo 
shyt) 
77 


/ 
! 
! 

! 
L 


Secis* 


This map shows that there could have been no crater lake 
before the eruption. The site of the present crater (cf. map on 
page 45) was occupied by three peaks whose position and 
altitude were determined with precision by the United States 
Coast and Geodetic Survey, from whose Chart N°. 8555 the 
figure is traced. 


recent outburst had intervened a pause probably many centuries in 
duration and when activity was resumed it differed materially from 
what had preceded. The Eruption of 1912 consisted entirely of 
fragmental products rather than molten lava. First came the great 
outpour of ash and pumice which is the subject of this note. Then 
Mt. Katmai blew up in a series of extremely violent explosions 
which left behind the present gigantic crater in place of the former 
mountain summit. The total quantity of rock that disappeared from 


44 


the top of Katmai during the eruption is estimated at 11,000 >< 10° 
cubic yards (8400 x 10° cubic meters). 

Associated with the change in the character of the activity was 
an equally great change in the composition of the magma concerned. 
The old lavas are dark-colored basic-andesites with a silica content 
of about 60 per cent. 

But the new magma is a white, acid rhyolite with 75 per cent 
of silica. 

This change in composition of the magma, while without any 
particular bearing on the point at issue here, is of great significance 
in interpreting other aspects of the eruption, for it enables us to 
gain considerable. insight into the processes operation before and 
during the explosions. 

A second line of proof that the Incandescent Sand Flow could 
not have been of the type supposed by Dr. Escuer is that the slopes 
of Katmai show no evidence of such a flow having passed over 
them. As Dr. Escnrr rightly asserts, a lahar erodes in the upper 
steep portion of its course. Erosion would have been particularly 
marked if such a flow had passed down the slopes of Katmai, since 
they were covered with ice, which would have melted away with 
ereat rapidity before a hot lahar. Yet the slopes down which Dr. 
Escuer assumes the lahar to have coursed are still clothed by the 
glaciers which originally covered them. To be sure, the heads of 
these glaciers were blown away in the explosions of the summit of 
the mountain and their toes were melted back by the flow of in- 
candescent sand across them from Novarupta down the Valley. But 
these accidents to the extremities only serve to emphasize the un- 
disturbed condition of the middle slopes down which the hypothe- 
tical lahar is supposed to have run. 

Instead of having flowed down the slopes of Katmai, the mass 
clearly moved transversely across the base of the voleano. The high 
sand mark, i.e. the edge of the flow, slopes steadily from south to 
north across the foot of Katmai. Its altitude at the south edge of 
the glaciers is several hundred feet greater than at the north edge, 
thus indicating that it flowed north along the foot of Katmai rather 
than westward from its heights. 

A third cireumstance which makes it impossible to assign the 
origin of the flow to Katmai volcano is the distribution of its material. 
A more detailed contour map then that published with Dr. Escumr’s 
argument (see page 45) makes it clear that the greater part of any 
fluid poured down the western slopes of Katmai would pass through 
the Kast arm of the Valley of Ten Thousand Smokes between Knief 


45 


Peak and Broken Mountain. A small portion might pass over the 
divide at Novarupta and run down between Falling Mountain and 
Baked Mountain. But as a matter of fact the quantity of flow material 


THE VALLEY OF TEN THOUSAND SMOKES 
FROM A SURVEY BY THE KATMAI EXPEDITIONS 
OF THE NATIONAL GEOGRAPHIC SOCIETY 
ROBERT F GRIGGS, DIRECTOR 
STUPROULATION AND TOROGRAPHY BY C.F MAYNARD 


Certain defin 
ontour intervals 200 ft 


oO 


Mt. Katmai and the Valley of Ten Thousand Smokes since the eruption. 
Compare Mt. Katmai with the map on page 43. The contours show that it 
would be impossible for a liquid flowing under gravity from top of Katmai 
volcano to reach the head of Mageik Creek via Katmai Pass. 


in the Valley leading away from the base of Katmai appears 
markedly less than that in the main arm of the Valley of Ten 
Thousand Smokes ten kilometers across the mountains from Katmai. 
No liquid starting from the summit of Katmai and seeking its level 
under gravity could possibly reach the summit of Katmai Pass. 

It is believed that the map on this page demonstrates this point 


46 


sufficiently. But it may be added that the relatively small scale map 
with contours no closer than 200 feet (60 meters) is much less 
convincing than an examination of the ground itself. I venture to 
assert that no one who had made field observations would have 
suggested the possibility of a flow from Katmai taking the course 
outlined by Dr. Escurr. The arrows on his map would make out 
that a part of the flow tarned out of the direct course and climbed 
the 150 meter slope between Falling Mountain and Trident, instead 
of continuing in a straight line down the Valley. Not only gravity 
but also inertia acting, as centrifugal force, would have opposed any 
such course. The presence of the flow in the saddle of Katmai Pass 
and down the slopes on both sides constitutes inescapable proof that 
part of it originated near the divide. A good-sized crater which 
may have been one of the points of origin les in fact near the 
summit of the pass. 

Any one of these three lines of evidence alone would negative 
the possibility of our flow being a lahar of the Klut type. Taken 
together they put such a hypothesis entirely out of the question. 

But, if the evidence definitely shows that our flow is not ana- 
lagous with the hot lahars of Klut, the determination of its real 
nature is quite another question. . 

In our earlier studies, recognizing the evident resemblance of the 
terrane to an ordinary mud flow, we sought to interpret it without 
assigning a very high temperature to its material — hence the 
descriptive name applied, “hot mud flow’. It was recognized from the 
first, however, that no ordinary aqueous suspension could ever 
convert a whole forest into charcoal. Further study made it more 
and more clear that the mass must originally have been very hot. 
Charred wood occurs only near the foot of the flow, fifteen kilo- 
meters or more from Novarupts. Throughout the main part of the 
Valley the vegetation was entirely consumed and its ashes dissipated. 
The rock of a whole mountain, named ‘‘Baked Mountain”, was 
changed from gray-green to brick red — as though subjected to a 
high temperature for a prolonged period. 

The stiffened tuff left behind after the sand flow: had come to 
rest differs materially in several respects from the deposits of Klut. 
In the first place it was much more viscous while in action. The 
average thickness of the Klut lahar is estimated as only 50 centi- 
meters. The pictures of destruction in Blitar all show a relatively 
thin veneer of volcanic debris covering the ground. This terminal 
portion moreover was not very hot as is evidenced by numerous 
plants with unwithered leaves standing close to the volcanic debris, 


47 


e.g. a patch of rank herbage beside the railway station at Blitar. 
(See this pag.) 
In our flow, on the other hand, the average thickness is fifty 


Photo from HeLtmic & Company. 
Volcanic debris from the Lahar of Klut at Blitar about 
5 km. above the termimus of the flow. The unburned 
buildings and unwithered herbage show that the lahar 
could not have been very hot at this point. 


times as great, indicating an entirely different sort of fluid. It is 
doubtful indeed if the minimum thickness of our flow was as low 
as the average thickness at Klut. Few, if any of the deposits lift on 
the ground are less than a meter thick. Clear out. to the very tip 
it retained an excessively high temperature. For a considerable 
distance beyond the present end of the flow material one finds 
stumps of bushes burned off by the heated material that once covered 
them but bas been eroded away. Outside the limits of the flow 
itself moreover all trees were killed for some distance and grass 
fires were started well down toward the tip. See pages 48 and 49. 

The deposits left behind, while different from the lahar of Klut, 
resemble closely those of the “incandescent avalanches” of Pelée 
and La Soufriere as deseribed by a number of observers, e.g. 
ANDERSON and Fierr’). 

This similarity together with the increasing evidence of a high 
temperature brought out by further study has convinced us as 
detailed by Fenner*) that the tuff filling the Valley of Ten Thousend 
Smokes originated as an outpour of red-hot material very much like 
the incandescent avalanches that rolled down the slopes of Pelee 
and La Soufriére in 1902. 

The differences between tlese and the hot sand flow with which 
we are dealing appear in fact to be due to differences in the cir- 


1)*Phik. Trans. Royal Society, A vol.200;%p. 492 et seq. 506 et seq. 
a )eOcpencit. p. O77. 


48 


cumstances of extrusion rather than in the character of the ejecta. 
Whereas the incandescent avalanches of the West Indian volcanoes 
issued from old vents of the central type, observations such as have 
been detailed in the case of Katmai exclude as possible source all of 
the five old volcanoes adjacent to the Valley of Ten Thousand Smokes. 


A section of the sand flow close to the terminus. 


Photo by L. G. Fotsom. 
The tree, about 30 cm. in diameter, was entirely reduced to 


charcoal. The material was much less fluid than the lahar of 
Klut, for it did not run out into a thin sheet as there, but 
remained relatively massive close to the extremity. (The sand 
is covered by stratified ash from Katmai and by outwash of 
the stream which later cut the section). 


49 


The configuration and practically continuous course of the high 
sand mark entirely around the Valley basin seem to leave no escape 


The edge of the incandescent sand flow of the 
Valley of Ten Thousand Smokes. 


Photo by P. H. HAGELBARGER. 

The picture was taken about the same distance, circa 5 km. 
above the terminus, as the one of Klut. Contrast the total de- 
struction here with the uninjured trees at Blitar. On the original 
surface where revealed by erosion may be seen the stumps of 
trees burned off just above the ground. 


from the conclusion that the material originated within the confines 
of the Valley itself, that the vents from which it issaed were located 
within the limits of the high sand mark. Since vents in this situation 
would be choked by their own products unless vigorously explosive ’) 
we need not be surprised if the points of issue are not certainly 
identifiable. 

The distribution of the flow, sloping as it does both ways across 
two divides, shows that it could not have come from any single 
vent. A number of considerations suggest that many vents, rather 
than a few, were probably concerned. The character and distribution 
of the present fumaroles in the Valley, togetlier with some other 
circumstances, likewise make it appear more probable that the ori- 
fices were fundamentally fissures, not centralized vents on the model 
of the ordinary volcano. 

The nature of the vents from which the incandescent material 


1) Since the type of material composing the tuff is strictly confined to the 
Valley basin, not a particle of it being found on the adjacent mountain slopes, it 
is clear that the magma must have issued comparatively quietly, albeit the material 
is now thoroughly fragmented, indicating a degree of inflation comparable with 
the magma of Katmai which exploded with great violence. 


50 


issued may, however, remain largely a matter of opinion, but their 
location within the Valley is, it is believed, definitely established. 

In conclusion, may I express my appreciation of the helpful spirit 
in which Dr. Escner has attempted to assist in the solution of what 
is admittedly a very perplexing question? I shall hope, moreover, 
that the necessity which IL have been under of showing that his 
thesis does not accord with the facts will not discourage further 
discussion of the remarkable phenomena of the Eruption of Katmai. 
For it is my belief that here is presented a unique opportunity to 
gain an understanding of the phenomena of volcanism; that there 
are problems here which, in their ultimate solution, will require 
the codperation of many minds approaching them from many differ- 
ent angles. : 


ERRATUM. 


In Prof. PrketHarine’s communication: “On the Movement of 
Pepsine, a.s.o.’ (Proceedings Vol. XXIV, p. 269) to read p. 272, 
2-4 jine from the top 1 mgr. instead of 0,1 mgr. 


KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN 
TE AMSTERDAM. 


PROCEEDINGS 


VOLUME XXV 
Nes, 3 and 4. 


President: Prof. F. A. F. C. WENT. 
Secretary: Prof. L. BOLk. 


(Transiated from: “‘Verslag van de gewone vergaderingen der Wis- en 


Natuurkundige Afdeeling,” Vol. XXXI). 


CONTENTS. 


H. J. VAN VEEN: “Axes of Rotation of Quadratic Surfaces through 4 Given Points”. (Communicated 
by Prof. JAN DE VRIES), p. 52. 


H. J. VAN VEEN: “Axes of Rotation and Planes of Symmetry of Quadratic Surfaces of Revolution 
through 5, 6 and 7 Given Points”. (Communicated by Prof. JAN DE VRIES), p. 61. 

P. ZEEMAN and H. W. J. Dik: “A Connection between the Spectra of lonized Potassium and Argon”. 
(First Communication), p. 67. 

J. W. N. LE HEUX: “Explanation of some Interference-Curves of Uni-axial and Bi-axial Crystals by 
Superposition of Elleptic Pencils’. (Third paper). (Communicated by Prof. HENDRIK DE VRIES), 
p. 81. (with one plate). 


J. W. JANZEN and L K. WOLFF: “Studies on the bacteriophagus of D’'HERELLE”, II (Communicated 
by Prof. C. EYKMAN), p. 87. 


G. HERTZ: “On the Mean Free Path of Slow Electrons in Neon and Argon”, (Communicated by 
by Prof. P. EHRENFEST), p. 90. 


G. J. VAN OORDT: “On the morphology of the testis of Rana fusca Résel”. (Communicated by Prof. 
J. BOEKE), p. 99. 

G. SCHAAKE: “A New Method for the Solution of the Problem of the Characteristics in the 
Enumerative Geometry”. (Communicated by Prof. HENDRIK DE VRIES), p. 113. 

W. H. KEESOM and J. DE SMEDT: “On the diffraction of Réntgen-rays in liquids”. (Communicated 
by Prof. H. KAMERLINGH ONNES), p._118. (With one plate.) 

N. H. KOLKMEIJER: “The crystal structure of germanium”. (Communicated by Prof. H. KAMERLINGH 
ONNES), p. 125. 

R. J. WOLVIUS: “An Objective Method for determining the Co-agulation-time of Blood”.(Communi- 
cated by Prof. A. A. HIJMANS VAN DEN BERGH), p. 127. 

F. J. J. BUYTENDIJK: “A contribution to the physiology of the electrical organ of 


Torpedo” 
(Communicated by Prof. G. VAN RIJNBERK), p. 131. 
RUDOLPH J. HAMBURGER: “On the Significance of Calcium- and Potassium-ions for the artificial 


Oedema and for the lumen of the bloodvessels”. (Communicated by Prof. H. J. HAMBURGER), 
p. 145. 


Erratum, p. 150. 


Proceedings Royal Acad. Amsterdam. Vol. X XV. 


Mathematics. — “Aves of Rotation of Quadratic Surfaces through 
4 Given Points’. By H. J. van Veen. (Communicated by 
Prof. Jan pr Vrits). 


(Communicated at the meeting of March 25, 1922). 


§ 1. If we assume three points in space, any straight line / may 
be considered as the axis of rotation of a quadratic surface of revo- 
Intion through these points. For the circles which the three points 
describe during the revolution round /, cut a plane through 7 in 
six points. These lie apparently on a conic &? which has / as axis 
of symmetry. Revolution of &? round / gives a quadratic surface of 
revolution (in what follows to be indicated by O*), which has / as 
axis of rotation (briefly axis) and which passes through the 3 given 
points. 

As a rule an QO? is defined by its axis and three points; if, 
however, during the revolution round / two (or three) of the given 
points describe the same circle, there exists a pencd/ (net) of O”s 
that have / for axis and pass through the 3 points. 

An 0? is always detined by 3 cireles with the same axis, provided 
these circles do not all lie in the same plane. 


§ 2. The axes of the O7’s through 4 given points A;(¢@=1...4) 
form a complex of rayes I, which will be investigated in what 
follows. By O* we shall understand a quadratic surface touching 
the sphere-circle y* twice; the line p joining the points of contact, 
will be called chord of contact; the conjugated polar line of 
p — defined as the locus of the points the polar planes of which 
pass through p — is the avis of O?. Asa rule this locus is a straight 
line p’ passing through the pole LP of p relative to y’; if p’ is 
indefinite only the straight line (or lines) conjugated to p and passing 
through P will be considered as axis. 

As special quadratic surfaces which according to the aforesaid 
must be considered as 0?, | mention: a parabolical cylinder with 
a plane pencil of axes in the plane Vo at injinity and a pair of 
parallel planes with a sheaf of // axes. 


53 


§ 3. Assume an arbitrary plane a and in it a point P. If Q is 
the point at infinity of a straight line of the plane pencil (P,a), PQ 
can only be the axis of an QV? touching y? in its points of inter- 
section with the polar line g of Q relative to y?, but at the same 
time the polar plane of P relative to the same 0’, must pass through g. - 

The 0”s through A; touching y? at its points of intersection with 
q, form a pencil; if Q moves along the straight line at infinity r 
of 7, g revolves round the pole & of 7 relative to y’. We get in 
this way o* 0*’s cutting V, in a system of ow” conies A? touching 
y’ at its intersections with a ray of the plane pencil round R. 

Now I represent the space of the conies of V on a five dimen- 
sional point-space R, by considering the coefficients of the equation 
of a &? as the homogeneous coordinates of a point in R,; to a 
conic A? and to a linear system of o* conies (k7), of Vy there 
correspond a point and a linear space FR; of R, and inversely. 

The double straight lines of a (47), of Vg envelop a conic; two 
of those double lines pass through &, hence the image of all double 
lines through & has 2 points in common with an arbitrary &,; it 
is a conic £,*. To y? there corresponds a point P and to the pencils 
touching y? in its points of intersection with rays of the plane pencil 
round #, there correspond the generatrices of the cone A’ that has 
P as vertex and £,* as directrix. 

All the quadratic surfaces through A; relative to which P and 
one of the straight lines g are harmonically conjugated, form a 
linear system of o* individuals, an (07),; this cuts Vg in a (4), to 
which there corresponds an &, in &,. Considering the quadratic 
surfaces through A; relative to which P and & and P and Vy 
are conjugated, it appears that the ,’s corresponding to all the 
straight lines g, pass through an FR, and lie in an R,. These R,’s 
cut the space FR, in which & lies, in a plane pencil the rays of 
which by means of the straight lines q are projectively associated 
to the generatrices of K. It happens three times that the associated 
elements coincide, hence there exist three 0?’s through A; that have 
a straight line q as chord of contact and the polar plane of P 
relative to such an 0? passes through g. To a plane pencil (2, 2) 
there belong therefore three rays of I or: 

the complex VU of the axes of rotation of the quadratic surfaces 
of revolution through 4 given powts is of the order 3, the complex 
cones are of the order three, the complex curves of the cluss three. 


§ 4. Algebraically the order of T may be found by determining 
e.g. the complex cone of an arbitrary point. With a view to this I 
4* 


54 


take this point as the origin of a rectangular system of coordinates. 
The equation of an arbitrary quadratic surface of revolution is: 
PF (eyy,2) =a? + yy? + 2? + @ (ae +by+c2)? +2 Axe +2 By+2C2+ D=0. 
The axis of revolution is defined by the equations: 
of of of 
or — Oy — 02 
a b Cc 


or 


dee ioe es ee ee 
a b a c 


and passes through O if 


Zl > Jes CG 
= a = B. 
a 0 Cc 


Consequently only the axes of the surfaces 

wv? fy? + 2? + a(ax + by + cz)? + 2p(aw + by 4+ ez) + y=0 
pass through O. 

We only consider ©O*’s through the four given points (aj, ¥;, 21), 
hence: 
a? + OF + 27 + a(axj+ byi + cz)? + 28 (ax; + byi +cz;)+y=—0; 
elimination of @, 8 and y gives: 

|v? + yi? + 2? (aaj + by; + cz)? ae; + by: + cz 1|=0 

As a,6,c are the direction cosines of an axis through O, they 
are proportional to the coordinates of an arbitrary point of such a 
straight line. Consequently the equation of the complex cone of O 
becomes : 

| a? y2 + 22 (wa, + yy + 22)? wai + yy: + 22; 1/=0. 

In a similar way an equation may be derived defining the rays 
of Tin an arbitrary plane. 


§ 5. If the origin of a rectangular system is placed at the centre 
of the sphere through Ai, the equation of the complex of rays in 
line coordinates may be written: 


OF Pe Pn Dame 
URE OL ile? Faron i! 
Py 3a, Shap ee: === |) 
Ei Le” ae we 
PP a, Ys Z, 1 | 


where Ps = p,ai + pyyit pyri: 


55 


§ 6. All the straight lines through the centre J/ of the sphere 2B 
passing through the points A:, are rays of I. Likewise all the straight 
lines perpendicular to a side plane of the tetrahedron 7’ that has 
Ai as angular points; for they are axes of the O? consisting of that 
plane and a parallel plane through the 4! angular point. Further 
any line perpendicular to 2 subtending sides of 7’ belongs to 1; they 
are the axes of the O° consisting of the pair of parallel planes 
through these 2 sides, hence: 

the complex T' has 8 cardinal points: M, the points D; at in pinity 
of the normals to the side planes and the points at infinity H; of 
the normals to the subtending sides of T. 


§ 7. If the points A; revolve round a straight line /, lying in 
a perpendicular bisector plane of a side of 7, 2 of the points Ai 
describe the same circle; from this follows that / belongs to T, or: 

the six perpendicular bisector planes of the sides of T are cardinal 
planes of T. 

I shall now show, that all the straight lines of V_ are double 


rays of I. 


§ 8. The axes corresponding to an arbitrary point P of V, belong 
to a pencil (07); they are the straight lines p’ conjugated to the 
polar line p of P relative to y’?. The centres of the individuals of 
the pencil lie on the polar line p of P relative to y? (they belong 
to the parabolical cylinder of the pencil) and on a conic passing 
through P and M and intersecting p. The axes through P form 
consequently a plane pencil in J”, and a pencil the plane of which 
passes through J/, hence: 

the complex TV consists of «* plane pencils of parallel rays lying 
in the planes of the sheaf round M. 

From this there follows that I is invariant for any homothetiec 
transformation relative to J/; the complex cones corresponding to 
the points of a straight line through J/, have accordingly the same 
enrve at infinity. 


§ 9. All the straight lines of V belong to I, hence the complex 
curve of an arbitrary plane « touches the /, of its plane. Besides 
this straight line one more tangent may be drawn to the complex 
curve out of each point P of this /,. namely the line of interseetion 
of a with the plane of the pencil of complex rays through P passing 
through MM. Consequently 2, is a bi-tangent of the complex curve 
of a and also of all the planes in which it lies, or: 


V carries a field of double rays of T. 


56 


§ 10. The complea curve of an arbitrary plane x is rational; the 
lL. of wis plane is its bi-tangent; single tangents are: the lines of 
intersection of x with the perpendicular bisector planes of T. 

Through its bi-tangent and the six single tangents the complex 
curve of an arbitrary plane is defined; other tangents may be con- 
structed with the ruler. 


§ 11. If the tetrahedon 7’ is cut by V,, we. get the well known 
contiguration of a complete quadrilateral. Polarisation of this figure 
in the absolute polar field gives a complete quadrangle having D 
as angular points; the straight lines at infinity of the perpendicular 
bisector planes are the sides and the points H; are the diagonal 
points of this quadrangle. 


§ 12. In a plane = through one of the points H;, hence parallel 
to a normal to 2 subtending sides of 7’, the complex rays consist of 
a plane pencil round H; and the tangents of a parabola. If x passes 
at the same time through J/, it contains atso a plane pencil round 
M, hence also a third plane pencil; as the /, of a is a double ray 
of I, the centre of this third plane pencil lies also on /, 

In a plane a through 2 of the points H; there lie plane pencils 
round both these points, henee also a third plane pencil; to this 
belong the points of intersection of a with the perpendicular bisector 
planes through the third of the points H;, hence: 

to IV there belong three bilinear congruences, which have as direc- 
trices the join of 2 of the pots H; and the line through the 3"¢ of 
the points H; and M. 

If a passes through 2 points H; and through J/, the complex 
rays in a form the plane pencils round these three points. 

In a plane a through one point /7/; and two of the points Di 
there lie three plane pencils of complex rays round these points. 
If « passes also through M it is a cardinal plane. 


§ 13. Before investigating the planes through a point D; I shall 
first consider the complex cone of a point P of the perpendicular 
m; out of M to one of the side planes of 7. This complex cone is 
apparently split up into three plane pencils, lying in the perpendi- 
cular bisector planes through m;; m; is a threefold generatrix of the 
complex cone of each of its points, hence: 

the four straight lines m; are 3 fold rays of T. 

In a plane a through m; lies a plane pencil round / anda plane 
pencil round D;; now the 1, of a is a double ray and m; is a 


57 


threefold ray of PF, hence the third plane pencil in a has likewise 
D; as vertex; the complex rays in a form accordingly a plane 
pencil round J/ and a plane pencil round /); which is to be counted 
double. 


§ 14. Consider an arbitrary plane a through one of the points 
D;; in this there lies a plane pencil of complex rays round D,, 
while the rest of the rays envelop a parabola. Out of each point P 
of the /, of a there can be drawn besides /, one more tangent 
to the parabola; P is the point of contact if this straight line coin- 
cides with /,. The plane of the pencil of complex rays through P 
passes in this case through Jf and through D;, hence through m,, 
but then P coincides with Di; or: 

in a plane through one of the points D; (// to a straight line mj) 
the complex rays consist of a plane pencil round this point and of 
the tangents of a parabola with axis // mj. 


§ 15. In a plane through J there lies a plane pencil of rays 
round this point and as the /, of this plane p is a double ray of 
I there lie 2 more plane pencils with centres P? on p. The points 
' P and the straight lines p are conjugated in a null system [2,1]. 
By conjugating to each other the points P lying on the same straight 
line, an involution of pairs [2| arises. This involution is quadratic, 
for on an arbitrary straight line there lies one pair of conjugated 
points. ; 

The involution [2] is not a quadratic inversion as the joins of 
conjugated points do not pass through a fixed point; consequently 
[2] consists of the pairs of points conjugated to each other relative 
to the conics of a pencil. This involution has 4 double points (the 
base points of the pencil), in this case the points D,, and 3 cardinal 
points, the diagonal points of the complete quadrangle of the base 
points, in our case the points H;, hence: 

the complex TU consists of pairs of plane pencils of parallel rays 
lying in planes through M. The vertices of the two plane pencils 
lying in the same plane, are conjugated points of a quadratic invo- 
lution in V,. 


§ 16. If a straight line p of V,, revolves round one of its points 
O, the points associated to p in the null system |2,1] deseribe a 
curve k* of the 3rd order; this curve passes through QO, through H, 
and touches the straight lines OD; at D;. The curves &* belonging 
to all the plane pencils of V_,, form a net with seven base points, 


H; and Dj. 


58 


§ 17. In order to get the complex cone of an arbitrary point P, 
we consider a plane 2 through J/P; let O be the intersection of 
MP, p the intersection of 2 with V,. If P, and P, correspond to 


p, PO, PP, and PP, are the lines of intersection of the complex 


o° 


cone of P with a. If a revolves round PO it appears that: 
the complex cone of a point P passes through the straight lines 
PM and PH; and touches the planes MPD; along the lines PD;. 
At the same time it appears again that if ? moves along a straight 
line through J, the curve at infinity of the complex cone of P 
remains unaltered (ef. § 8). 


§ 18. Out of a point O, 4 real tangents OD; may be drawn to 
the corresponding curve 4°, hence the curves k* and also the complea 
cones consist of two parts. 

The caracteristic of a curve * is defined by the 4 straight lines 
OD;. Through D; there pass 3 conies through the points O of which 
there pass 4 harmonical rays through Dj, hence: 

the locus of the points with harmonical complex cones consists of 
3 quadratic cones the vertices of which he in M and which pass 
through the straight lines mi, and also: 

the complex cones of the pownts lying on a quadratic cone through 
the 4 straight lines m;, have the same characteriste. 


§ 19. The curve of Jacopi of the net of the curves 4° consists of 
the six sides of the complete quadrangle of the points D,. No rational 
curves £* belong to the net, only curves degenerated in a side of 
the quadrangle and a conic through the 4 points D; and H; that 
do not lie on this side, accordingly : 

there are no points with rational complex cones; for any point of 
a perpendicular bisector plane the complex cone degenerates into a 
plane peneil and a quadratic cone; for a point V, the complex cone 
consists of a plane pencil in V,, to be counted double, and a single 
plane pencil. 


§ 20. As each complex curve has a double tangent, we might 
call those planes where the double tangent is an inflexional tangent, 
singular planes. In this case the two points P corresponding to the 
straight line p in the null system [2,1], must coincide. This happens 
only when a plane a passes through one of the points D;, but 
then the system of complex rays in a splits up into a plane pencil 
and the tangents of a parabola; consequently non-degenerate complew 
curves with an inflexional tangent do not occur. 


59 


§ 21. If in a there lies a plane pencil with centre P at finite 
distance, there are also 2 plane pencils with their centres on the 
1, of a: if a does not pass through one of the cardinal points at 
infinity, the planes of these latter pencils pass through J/, hence: 

only the planes through the 8 cardinal points contain degenerate 


complex curves (ef. §§ 12, 13 and 14). 


§ 22. As the null system [2,1] and the involution [2] are 
invariant for central projection, we can construct the complex cone 
of an arbitrary point P in the following way : 

We determine the points of intersection D; of the perpendiculars 
out of P to the side planes of 7’ with an arbitrary image plane r 
and also the intersection O of 7M with tr. Then we construct the 
double points of the quadratic involution in which the conics of the 
pencil through D; cut an arbitrary straight line / through O; we 
fix this involution by means of the points of intersection of / with 
2 degenerate conics of this pencil. The straight lines joining P to 
the double points in question, are generatrices of the complex cone 


Giele 


§ 23. If the points A; are coplanar, their plane @ cuts an ©? of 
the system in consideration along a conic 4? through A; or is a 
part of the 0. In the first case the axis of O* lies in one of the 
planes through the axes of symmetry of £* perpendicular to «; in 
the second case the axis of U* is a straight line perpendicular to «. 
The axes of symmetry of the conics through A; are tangents to a 
curve of the 3 class touching the line /, of « twice; the planes 
through these axes and y @ touch a cylinder of the 3'¢ class with 
V,, as double tangent plane. 

The rays of Fin an arbitrary plane a touch also in this case at 
a curve of the 3°¢ class that has the 7 of its plane as a bitangent. 
The complex cone of an arbitrary point P, however, splits up into 
3 plane pencils the planes of which touch at the cylinder in question ; 
a perpendicular to « is a triple generatrix of the complex cone of 
each of its points, hence: 

if the 4 points A; are coplanar, I consists of the tangents to a 
cylinder of the 374 class; V, is the bearer of a field of double 
rays; the vertex of the cylinder at infinity is the bearer of a sheas 
of triple rays. 


24. Now consider the case that 3 of the points A; lie on a 
I 
straight line a; then the O?’s must pass through a fixed point 4 


60 


and a fixed straight line a. If A is to lie on the quadratic surface 
which @ deseribes when it revolves round a straight line /, the circle 
which A describes when it revolves round /, must cut the straight 
line @; accordingly / must lie in the plane which bisects perpendi- 
cularly the straight line joining A to a point of a. These planes 
touch a parabolical cylinder that has for directrix the parabola of 
which A is the foeus and a the director line and the generatrices 
of which are perpendicular to the plane (4,q). 

If a revolves round a straight line crossing it at right angles, a 
plane is produced which, completed by the plane through A parallel 
to if, gives another (* that satisfies the conditions mentioned, hence: 

if three of the four points A; are collinear, [ splits up into a 
pencil of rays with the axis at infinity, and the tangents to a para- 
bolical cylinder. 


Mathematics. — “Aves of Rotation and Planes of Symmetry of 
Quadratic Surfaces of Revolution through 5,6 and 7 Given 
Points.” By H. J. van Veen. (Communicated by Prof. 
Jan DE Vrigs). 


(Communicated at the meeting of April 29, 1922). 


§ 1. Let there be given five points 4, A, B; (j= 1, 2, 3). I consider 
the complexes I, and TP, belonging to the points A, B, and A, B,'). 
Generally a common ray / of TY, and 1, is the axis of an 0? through 
the 5 points; for / is the axis of an 0? through A, B; and of an 
O* through A, B;; these two 0?’s have in common the 8 parallel 
cireles on which the 5; lie; hence they coincide. An exception 
exists for the straight lines in the perpendicular bisector plane of 
the join of 2 of the points B;, and also for the straight lines of 
V_,. The field degree of the congruence of axes is therefore 

3.3 —3 — 2.2 = 2. 

At the same time there must be split off: the sheaf of the rays 
which are perpendicular to the plane through the points B;. Let D 
be the centre at infinity of this sheaf; both the complex cones of 
a point P touch the plane through P M/, M, and D along P D, hence: 

the axes of the Os through 5 given points form a congruence of 
the sheaf degree 7 and the field degree 2, C%". 


§ 2. To C% belong the complex rays of I, lying in the perpen- 
dicular bisector plane of a straight line A, B;, hence: 

the 10 perpendicular bisector planes of the joins of the 5 given 
points are singular planes of the order 3. 


§ 3. In the two null systems belonging to P, and I, the curves 
k,* and k,* (Os through 4 points § 16) are associated to a plane 
pencil round a point O of V.,; these curves pass through OQ, 
touch O D at D and have accordingly six more points in common. 
Consequently through O there pass six straight lines on which the 
two pairs of points which through the two null systems are asso- 
ciated to them, have one point in common. 


1) Cf. my paper “Axes of Rotation of Quadratic Surfaces through 4 Given 
Points.” 


6: 


The complex curves in an arbitrary plane through such a straight 
line touch each other at the point in question, so that the two 
complex curves have 5 coinciding tangents in common in the 2, 
of their plane. Now we have split off the straight lines of V_ as 
4-fold rays of the congruence of the intersection of the two com- 
plexes, hence: 

Vw a singular plane of the order 6. 


ao 


§ 4. We can also arrive at this last result in the following way. 
The quadratic surfaces through 5 points form a linear system of 
| § | A 
individuals; these eut V. in a (d"),; the conie of the double 
ea 4 


straight lines of this (47), belongs to the parabolical cylinders of 


fo oft 


(O?), Let C be such a eylinder, 7’ its vertex, c the line along which 
C touches V_. 

The polar plane of 7’ relative to C is indefinite, hence 7 has a 
fixed polar plane relative to all O*’s of the pencil through 4, B;, 
which touch y? in its points of intersection with ¢. This fixed polar 
plane is at the same time the plane of the centres of the individuals 
of the pencil; it passes through the polar line p of 7’ relative to 
y’. In the null system [2,1] belonging to I, the pole Pofce relative 
to y? is associated to p. 

As the fixed polar plane of 7’ relative to the O”s through A, B; 
that touch y’ at its points of intersection with c, pass likewise through 
p, in the two null systems corresponding to TP’, and Pr, the point P 
is associated to p. 

P was the pole of c relative to y?, hence the locus of P is a 
conic. The order of the null systems is three; accordingly the locus 
of the straight line p is a curve of the sixth class. 

We remark also that to each parabolical cylinder one axis in 
V, remains associated (07's through 4 points, § 2), namely the 
polar line of its vertex relative to y?. 


§ 5. If sw points are given I consider a group of 4 and a group 
of 5 of these points which have 38 points in common. To the 
group of 4 points there belongs a complex I”, to that of 5 points 
a congruence C©7?. The axes in question are part of the common 
rays of complex and congruence; however, we must split off: the 
tangents of three curves of the 3rd class and twice the tangents of 
a curve of the sixth class, so that we arrive at a ruled surface of 
the order 3(7 + 2) — 3.3 — 2.6 = 6, hence: 

the aves of the O's through six points form a ruled surface of 

6 


the sixth order, o°. 


Ss 


63 


§ 6. Through consideration of the perpendicular bisector plane of 
the straight line through the 2 points that belong to the group of 
5 and not to the group of 4 points, we find that in this plane and 
accordingly in each of the 15 perpendicular bisector planes, there 
lie 2 generatrices of 9°. 

The quadratic surfaces through six points cut V, in a linear 
system of o* conics (X?),. These define together with y? a linear 
system (4*),; the tangents of the conic of the double lines of (4°), 
are the chords of contact of the O7’s through the six points; polari- 
sation of these straight lines relative to y* gives a conic 4?; to (47), 
there belong four double lines, originating from parabolical cylinders 
(ef. § 4), so that the locus of the axes has a conic £* and 4 straight 
lines in common with J’,, hence: 

e° is rational; it has a double curve of the order 10; the 15 perpen- 
dicular bisector planes of the joins of the six points are bi-tangent 
planes; V,, is a 4-fold tangent plane. 


§ 7. In order to investigate the axes of the O7’s through seven 
points, we consider a group of 4 and a group of 6 of these points 
that have 3 points in common. We get in this way a complex I, 
and a ruled surface 9° that have 18 straight lines in common. If we 
subtract from them three times two straight lines lying in the 
perpendicular bisector planes of the joins of the 3 common points, and 
twice 4 straight lines in V,_, we have 4 straight lines left, hence: 

through 7 points there pass 4 O*'s. 


§ 8. We can also arrive at this result in the following way. All 
quadratic surfaces through 7 points cut V, in a (X7),; in connection 
with y? this gives a (47), with 4 double straight lines, consequently 
in (k?), there are four individuals touching y* twice. These belong 


to the surfaces of rotation through the 7 points. 


§ 9. A quadratie surface of revolution O? has a pencil of planes 
of symmetry passing through the axis of rotation and therefore 
defined together with this axis, and further generally one more plane 
of symmetry perpendicular to the axis. I shall investigate these latter 
planes for O's through given points and I define as a plane of 
symmetry of an O the polar plane of the point P at infinity of 
the axis of rotation; if this polar plane is indefinite the planes 
through the chord of contact p ot the O* are considered as planes 
of symmetry. 


64 


§ 10. An arbitrary plane a is a plane of symmetry of one 0? 
through four given points A;; for through A; there passes a pencil 
of O*s touching y? at its points of intersection with 2; generally 
one of these O*’s passes through the mirror image of one of the 
points A; relative to a and this surface satisfies the conditions. 

It may happen that the mirror image in question lies on the base 
curve of the peneil; then w is a plane of symmetry of all indivi- 
duals of the pencil. As the sphere 46 through A; belongs to the 


pencil, * must pass in this case through the centre J/ of this sphere. 


§ 11. The o* planes. of symmetry of the O*’s through /ive points 
envelop a surface of which I shall determine the class. The O's the 
planes of symmetry of which pass through a point P of V,, eut 
’, along conies that touch y? at its points of intersection with a 
ray of the plane pencil round P. The image of all such conics in 
R, is a quadratic cone K (Os through 4 points  § 3). 

The quadratic surfaces through the 5 given points cut into V_ 
a (k*), that has an R, as image in F,; this R, cuts K along a 
conic Ay. 

To the degenerate conies of V, there corresponds in R, a cubic 
hypersurface,» V*,, that has a double surface Ot, of the 4 order 
(a surface of Veronese). Besides its two points of intersection with 
k?; (O”s through 4 points, § 3) that lie on O*,, 47,7 has 2 more 
points in common with V*,, hence to the O*’s through the 5 given 
points the planes of symmetry of which pass through P, there belong 
two paraboloids of revolution; these have V, as a plane of sym- 
metry. Through a ray p of the plane pencil round P there passes 
one more plane of symmetry that does not coincide with V,, 
consequently the planes of symmetry through P envelop a cone 
that has P for vertex and that touches V,, twice. An arbitrary 
straight line / through / bears therefore 3 planes of symmetry ; 
through a line of V, there passes besides V, only one more plane 
of symmetry, hence: 

the planes of symmetry of the O's through 5 given points envelop 
a surface of the 3™ class of which V, is a double-tangent plane. 


§ 12. The conic along whieh this surface touches V,, has six 
tangents that are the bearers of pencils of tangent planes; these 
cannot belong to different O?’s for in that case through the 5 given 
points there would pass a pencil of O*’s touching y? at its points 
of intersection with a straight line p and from this would follow 
that the 5 given points must lie on a sphere. 


65 


To each of the six straight lines p belongs therefore one (? that 
to) I fo) 
has a pencil of parallel planes of symmetry, or: 
through 5 given points there pass six cylinders of revolution; their 
g I y ; 
generatrices are parallel to 6 sides of a quadratic cone. 


§ 13. The planes of symmetry through an arbitrary point touch 
a cone of the 3" class; let a be such a plane through the centre 
M of the sphere & through 4 of the 5 given points; a is then a 
plane of symmetry of an (* through the 5 points and also of the 
sphere B, hence of a pencil of O*’s through those 4 points, or: 

through the centre of the sphere through 4 given points there pass 
co planes each of which is a plane of symmetry of a pencil of O*'s 
through those 4 points; these planes envelop a cone of the 3” class. 

Such a plane z is also a plane of symmeiry of the base curve 
of the corresponding pencil, consequently to this pencil there belongs 
a cylinder of revolution of which the generatrices are perpendicular 
to a, hence: 

through 4 points there pass «* cylinders of revolution of which the 
generatrices are parallel to the generatrices of a cone of the 3™ order. 


§ 14. If six points are given, we consider two groups of five 
points; these have 4 points in common. The surfaces of the 3" class 
corresponding to these two groups, have in common the tangent 
planes of a developable surface of the 9" class that has V7, as a 
4-fold tangent plane. However, we must subtract from this the 
tangent planes through the centre of the sphere through the 4 com- 
mon points, hence: 

the planes of symmetry of the O's through six given points envelop 
a developable surface of the 6% class that has V, as a 4-fold 
tangent plane. 


§ 15. The quadratic surfaces through six points cut V7 in a 
(k?),; to this there belong 4 double straight lines; how many degene- 
rate curves touching y? twice, belong to (47), ? 

In order to determine this number we remark that the cone in 
R, formed by the straight lines joining the image of y? to O*, 
(§ 11), cuts thé image R, of (k?), along a curve /* of the 4% 
order; this curve has besides the 4 points that are the images of 
the double lines of (47), and that are to be counted twice, 4 more 
points in common with V*,, hence: 

through six points there pass 4 parabolical cylinders and 4 para- 
boloids of revolution. 


66 


As through an arbitrary point P of V., there pass 2 more planes 
of symmetry, (for the conie of the double lines of (47), defined by 
y? and (7), sends two of them through P), we find also in this 
way, that the planes of symmetry in consideration envelop a 
developable surface of the sixth class with V., as a 4-fold tangent 
plane. 


§ 16. In order to find the planes of symmetry through seven 
given points, we consider a group of six and a group of five of 
these points that have 4 points in common. The corresponding 
surfaces have 3.618 tangent planes in common. If we subtract 
from them 2.4—8 times JV, and further 6 planes through the 
centre of the sphere through the 4 common points, it appears 
again that: 

through seven given points there pass 4 quadratic surfaces of 
revolution. 


(Cf. §§ 7 and 8). 


Physics — “A Connection between the Spectra of Tonized Potas- 
stum and Argon.” (First Communication.) By Prof. P. Zeeman 
and H. W. J. Dik. 


(Communicated at the meeting of April 29, 1922). 


According to the conception of RurHerrorD-Bonr an atom consists 
of a very small positively charged nucleus, which contains almost 
the whole mass of the atom, and of a number of electrons revolving 
round the nucleus. The number of electrons moving round the 
nucleus, is equal to the atomic number of the element; hence this 
also indicates the number of units of charge which an atom that is 
neutral taken as a whole, possesses in the nucleus. 

It has. been made plausible that the electrons are arranged in 
shells or sheaths with the nucleus as centre. In particular the regular 
changes which the chemical properties undergo with the increase 
of the atomic number, make this probable. Regularly elements occur 
in the periodic system which easily cede one electron (the alkalis), 
regular is also the succession of the inert gases. This becomes com- 
prehensible when it is assumed that a shell can become full, and that 
then the configuration will be very stable: helium, neon, argon ete. 
The atoms of lithium, sodium, potassium ete. have only one electron 
in the outer shell. On this similarity in structure rests also the 
resemblance which has been observed at an early date in the are- 
spectra of the alkalis. The one outer electron can be removed by 
the electric forces which are active in a spark. Then the atom is 
ionized, and the electron combination which has remained, can emit 
the spark spectrum. 

On these general features of the atomic model, in particular on 
the number of outer electrons which increases at every step in the 
periodic system, rests a displacement law enunciated by KossrL and 
SOMMERFELD’), which establishes a connection between the spark 
spectrum of an element and the arc-spectrum of another element 
which precedes it in the periodic system. If e.g. an electron of the 
potassium-atom has been driven out, the remaining electron system 
must present the greatest resemblance with that of argon, and only 


1) KosseL u. SOMMERFELD, Auswahlprincip und Verschiebungssatz bei Serien- 
spectren. Verh deutsch. physik. Gesellsch. 21. Jahrgang 240, 1919. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


68 


differ from it in that the positive nucleus of potassium possesses 
one unit of charge more. Like the are-spectrum of argon, the spark- 
spectrum of potassium must be composed of a great number of 
lines, and not show series. As yet the relation which the displace- 
ment law renders probable, is only qualitatively known. 

Kor some time some researches have been in progress in the 
Amsterdam laboratory to determine the relation quantitatively. 

We will here communicate some results to which the investiga- 
tion of potassiwm has led. These faets retain their value whatever 
interpretation may have to be given to them. 

Besides the are-spectrum of potassium with the so well-known 
spectrum series which according to SOMMERFELD’s Opinion originates 
from the neutral atom, Eprer and Vanenra') observed in 1894 a 
spectrum, emitted by ionized potassium, which was very riehl in 
lines. Eper and Varenta observed simultaneously are- and spark 
lines; in 1907 Gorpstrin?) however, succeeded in observing in the 
intensely luminous line of discharge occurring in the passage of vigor- 
ous electric discharges through powdered salts, a spectrum in which 
only lines are seen which have not been ranged into series, and in 
which even the distinct are-lines did not appear. GOLDsTEIN points 
out that these lines owe their origin to circumstances which differ 
essentially from those which give rise to the are-lines, and he 
introduees the name of ‘ground’ spectrum. We are undoubtedly 
justified in attributing the ground spectra to the emission of the 
once ionized atom. 

In the subjoined Table | a * denotes the strongest lines, those 
published by GonpsTE.n. 

With better appliances Eprr’s pupil Scumiincer*) could supple- 
ment GoLpstEn’s observations by investigating also the ultra-violet. 
He worked with vigorous discharges between potassium electrodes 
in a bulb with hydrogen. His observations are given under § in 
Table I. 

In 1915 some observations of NetrHorpn*) were published for 
potassium lying between 63807 A and 3898 A. He employed 
another type of tube than Gonpsrrin, and recorded-by means of a 
spectrograph. On his plates the arc-lines are absent, the ground- 
spectrum of GoLpsrrin coinciding with his strongest lines. The 
doubt expressed by Kayser whether Gorpsrein’s failure to see the 


1) EpeR u. VALENTA, Denkschriften Wien. Akad. 61. 347, 1894. 
*) Gotpstein, Verh. deutsch. physik. Ges. 321. 1907; 426, 1910. 
3) ScHILLINGER, Wiener Sitz. Ber. 118 [2a] 605. 1909. 

4) NettHorPe. Astropk. Journ. 41. 16. 1909. 


TABLE I. 


EV 


— © Oo © 


Intensity. 


s |x McL} D 


- OD ow oO 


69 


Potassium lines with electrode less discharge. 


H- 


+ 


+ 


+ 


Ht 


+ 15165 
15557 
15855 


16009 
16340 


17324 


17715 
18064 
18286 


18817 


19778 


Remarks 


Arc-line 


Py 
H 6563? 


Q 


Arc-line 


> 


Arc-line 
> 


Arc-line 


Py 


70 


TABLE I (Continuea). 


Intensity. 
Az y Remarks. 
EV| S | N |McL]) D 
27) Wa NS 15 5005.5 * 19978 Rs 
1;/—|;—|— 4965.5 Arc-line 
—|--}—-|— 4958 > 
1 1 | — 5 4943.2 20230 Ps 
—|—/]—]/ 3]/— 4863 Arc-line 
3] 2a 12 30 4829.2 * 20707 
—|/—/;]-—] 1/- 4805 Arc-line 
—}—|]—]}] 1]— 4190 > 
—|—}|—} 1)/=— 4769 
—}—|/—] 1J=— 4760 > 
—|—|/]—] 1] 3 4744 21079 Qs 
— | ee 1 |) 4720 
—/—!—|] 1l}— 4688 
3) 15 4659.8 21460 Ry 
2};—|]/—|;}-—|- 4650.7 
—{/—|—] 1l})= 4643 Arc-line 
6} 4] 15 30 4608.5 * 21699 
—|—]—]—] 10 4596.0 21758 Py 
5) 4 a8 30 4505.6 * 22195 P, 
| Bl 8) 20 4467.5 * 22384 Px 
10 | 4455.5 22444 Py 
ey a 10 4423.6 22606 Q6 
3) |Salel0 30 4388.3 * 22788 
—|—|—] 2] 10 4365.1 22909 Pio 
=) 4/35 30 4339.9 23042 Q; 
| Bill xe 30 4309.5 : 23204 Py 
7a \) Ship 2 30 4305.0 23229 Qs 
_ 1 | — 9 4288.6 23317 
—|—|/=+]—|] 8 4285.1 23337 Qo 


71 


TABLE I (Continued). 


Intensity. 
A y Remarks. 
EV; S | N |McL} D 
6| 8/ 10 30 4263.5 * 23455 Rs 
6| 4] 6 30 4225.7 Me 23665 Qn 
Go F548 30 4223.2 | 23679 
1}; 1]— 9 4208.9 23759 Qi2 
8 | 10 | 20 30 4186.2 * 23888 R; 
Gui) Du} 10 30 4149 1 * 24102 Pi 
6 | 5 |. 10 30 4134.7 * 24185 Rio 
4] 3] 10 30 4115.1 * 24301 Se 
—};—| &)—)}]— 4106.8 
—|—| TT} 1| -- 4104.2 
—}-—-| 3/—]— 4098.6 
== |) Sy oe 15 4093.5 24429 Pis 
—/—]}] 2}/-—]— 4086.8 
—|—| 3/-|— 4075.6 
ai A Ba ee 4072.3 
=|! ily) 10 4065.2 24599 Rio 
=| Bye — 4058. 1 
10 | 10 | — -- 4047.4 Arc-line 
10 | 20 | — — 4044.3 Arc-line 
oa eae 15 4042.5 24737 Piz S7 
eS 10 4039.9 24753 
1} 1}— 10 4024.9 24845 Pigs 
Ni lp | eeet 9 4018.9 24882 Pig 
roy 10 4012.2 24924 Ss 
Gy) 5.) (8 15 4001.1 24993 Pao So 
al], Zo] 8} 10 3995.0 25031 Sto 
=|) =|] = 8 3992.0 25050 Po, 
3 | 3B] «4 15 3972.8 25171 P22 
41) 3) 15 3966 7 25210 Pa3 


72 


TABLE | (Continued). 


Intensity. 
= = 7 y Remarks. 
EV| S | N |McL} D 
(ei 
4| 4| 8 15 3055.5 25281 Qis 
2i\ 01h |e 10 3943.3 25359 Si 
Wl) He} 9 3934.6 25416 
wail be 2 9 3927.3 25463 Sia 
Nol ital 9 3923.8 25485 Pog 
8| 8| 10 15 3898.0 25654 
—|— =| 2 3887.2 25726 Qis 
fl |) 5 3884.5 25743 Si3 
18)\ 8 3879.2 25779 Py; 
alee 10 3874.5 25810 Rig 
iP a 10 3861.9 25894 Qo, 
—|— a3 3844.8 26009 Pog 
12 15 3818.6 26187 Poy 
1 _ 3816.9 
yey 15 3800.8 26310 Rig 
3) || 3 15 3783.2 26433 Riz 
elee 15 3767 1 26546 Rig 
Aisle 6 3756.0 26624 Qs 
19 — S| 3749.1 
1) 4 9 3745.2 26701 Roo 
Fea 9 3739 2 26744 Rat 
ib): = ee 3727 5 
—| 1 9 3722.1 26866 Ro» 
Die 9 3716.9 26904 ; Ras 
1 Sh 3713.2 
Shi = 3683.7 | 
4| 4 15 3682.3 27157 Sis 
—| 1 8 3677.6 27192 Pog Rog 
Tell 10 3670.2 27246 P39 


73 


TABLE I (Continued). 


Intensity. 
7 y Remarks. 

EV| S | N'|McL| D | 
2 Ade) — 3660 
= SANG | 3650.6 27393 Sis 
=A) 14 4 3639.8 27474 Ras 
==. 9 3627.1 27570 Qos 
Ble sD | 15 3618.4 27636 P31 
ees) 12 3609.4 27105 Roe 
= ie 2 3593.8 27826 
= ie) 2 3587.1 27878 Ro; 
2a i* fem ees 3572 
25a 8 3562.5 28070 Ba 
auihig 20 3530.9 28321 Se 
= ji i 3518.8 28419 Rog 
er 7 3514.0 28458 P33 
= ae 3489 
rd laa | 8 3481.3 28725 Pe Se 
PA 8 3476.9 28761 
aed 1 3468.7 28830 Pag 
= ah 2 3457.8 28920 Qs» 

2 1 3447.5 29006 Arc-line 
i 3 = 3446.5 > 
6| 3 12 3440.5 29065 
Tange 10 3433.7 29123 P37 
—|1 8 3422.4 29219 
1. = sa |g 3421.5 29227 
2| 2 10 3404.7 29371 P3e 
—/ 1 7 3393.2 29471 P39 
6| 4 10 3385.3 29539 | Qn 
6| 4 10 3381.4 29573 Qss 
ie 10 3374.0 29638 Pyo 


74 


TABLE | (Continued). 


Intensity. 
A y Remarks. 
EV| S| N |McL} D ; 
—| 6 ve 3364.7 29720 
1| 8 ) 3363.4 29732 oo 
—| 2 7 3359. 1 29770 R32 
2 1 3357.2 29787 Sa 
8| 5 6 | 12 3345.8 29888 Py 
=| = ai) il 3337.7 29961 
1 | — —|— 3326.4 
1a era Bal 1G) 3322.1 30101 Py 
3] 4 5] 9 3312.8 30186 S31 
—|— Syelll “1 3302.0 30284 
3| 3 511/39 3291.1 30385 R34 
= 4 — 9 3289.1 30404 
=i || 74) By Il a 3278.8 30499 P43 
2 Sh G 3262.0 30656 
—|— 3) |) al 3258.8 30686 
| — 2 3253.9 30732 Qu 
—| 2 ah) 3241.1 30854 
Uf 4 iV M38) 3224.8 31010 S33 
Pi 2 —| 8 3220.9 31047 
1 _ 1 3219.1 31064 R3g 
2) |\eal — | — 3217.5 Arc-line 
1] 4 —| 5 3209.1 31161 R39 
—|— 4|— 3205.6 
Wp —!| 6 3202.1 31230 S34 
74 \| 2 —| 6 3190 6 31342 Ryo 
—| 2 SHG 3188.3 31365 S36 
= — 2);— 3174.0 
oy al 4| 3 3170.0 31546 
Tle Sale 3157.6 31670 S37 


75 


TABLE I (Continued) 


Intensity. | 

—ea 7, y Remarks. 
EV; S ee ee ee N |McL} D 

=e yi) yet 2|)— 3148.6 

3) — —-ji- 3143.7 

Ei ae 4) 5 3129.5 31954 

5| 4 6| 6 3105.4 32202 Rus 

Le kyat —|}—- 3103.1 

1) ad 2|— 3074.6 

1) — —|-— 3067.3 

Oi) es Sil S 3062.6 32652 Sy2 


said are-lines might possibly have to be attributed to a less good 
observational power in the extreme red and violet, appears therefore 
unfounded. 

The importance of the ground spectra made it desirable to perform 
new measurements. The best method to obtain the first spark 
spectrum of potassium in great parm and completeness we found 
to be exciting the luminosity of very diluted incandescent potassium 
vapour under the influence of very ‘rapidly varying electrical forces. 

When our investigation was in progress, there appeared a publi- 
cation by Mc Lennan') on the spectrum of ionized potassium. 
His tables present a close resemblance to ours, but in his Table | 
Mc Lennan gives the lines which he has observed besides those of 
ScHILLincer. Hence he also finds the are-lines, which we succeeded 
in eliminating. 

Besides both in his and in Scat.Lincrr’s observations a few important 
lines are wanting. Important because they have been serviceable in 
the search for the regularities to be mentioned presently. By the 
aid of Table | it is possible to compare the measurements of our 
second (D) with those of the other observers, besides the data in the 
column “remarks” show which P,Q, ete. could only be determined 
by the new lines. At the same time it is at once clear which of the 
lines are arc-lines. We estimate the accuracy of the measurements 


1) Mc Lennan, Proc. R. S. Vol. 100. 182. 1921. 


76 


from 4700 A at 0,2 A. To some lines a + is added to show that 
they ave not sufficiently accurate. (Cf. Table 1). 

Argon can emit two types of spectra. One is the so-called red 
spectrum, which is formed under the influence of weak electric 
forces, and must, therefore, be called the are-spectrum of argon. 
The other is formed by strong electric discharges, and is called the 
blue spectrum because of its colour; it is the spark spectrum of 
argon. No spectrum series are known in the red spectrum, but it 
exhibits the regularity found by Rypspure') that for 4< 4704 A 
the frequencies of almost all the lines may be arranged in a Table 
the four columns of which present a constant difference. Pavison ”) 
extended these results to the less refrangible part of the spectrum. 
Ryppere’s and Pavrson’s tables are reproduced here in Table II, 
somewhat abbreviated, but with continuous notation. It gives the 
constant differences for the wave-lengths of 29233—3319 Ne (Cf. 
Table II). The relations are: 

B=A+ 846,1 
C= A+ 1649.3 
D= A + 2256,1 

The frequencies in Table Il followed by an M have been taken 
from Mucecers*). They are more accurate than the frequencies in 
the original tables of RypBwra and Paurson. For this reason the 
mean value of Mrccurs has been put at the head of the Ay-column 
and not the mean value of all Av’s. 


The spark spectrum of potassium possesses the same property 
RypperG found in argon, for the examined region between 6594— 


3063 A. This appears from Table III, which has been obtained by 
the aid of the data in Table I. Under the heading “Remarks” in 
Table I the lines inserted and arranged in Table III are indicated 
by symbols (See Table III). 
The relations for the lines of ionized potassium are: 
Q=P+ 847 ; 
R= P+1695 i 
S= P+ 2542 
The first spark spectrum of potassium is, therefore, still somewhat 
simpler than the red spectrum of argon, the differences being: 


') RypperaG. On the constitution of the red spectrum of argon. Astroph. Journ. 
Vol. 6. 338. 1897. 

2) Pautson, Physik. Z. S. 15. 831. 1914. 

5) Meaamrs, Scientific Papers, Bureau of Standards N°, 414, 1918 


77 


TABLE II. Are-Spectrum of Argon. (RYDBERG and PauLson). 
Ne} A | | gape |a-tes6.2| aor | a+ tea | 6ose | A + 2056. 
1 10353 .2 607.3 | 10960.5 
2 11533.6 M | 803.1 | 12336.7 M | 606.8 | 12943.5 M 
3 | 10837.7 M” (1649.3) | 12487.0 M | 606.8 | 13093.8 M 
4 11896.7 (1410.4) | 13307.1 
5 | 11731.9 M | 846.2 | 12578.1 M (1409.9) | 13988.0 M 
6 | 11889.9 M (1649.2) | 13539.1 M | 606.8 | 14145.9 M 
7 | 12096.6 M | 846.2 | 12942.8 M | 803.0 | 13745.8 M | 606.9 | 14352.7 M 
8 | 12477.0 (2258.1)) 14735.1 
9 | 13326.2 (2258.5) | 15584.7 
10 15012.9 606.7 | 15619.6 
11 | 13668.4 847.9 | 14516.3 (1410.3) | 15926.6 
12 15429.3 606.7 | 16036.0 
13 | 14223.7 (1651.8) | 15875.5 
14 15078.3 (1409 9)| 16488.2 
15 | 14413.4 (1651.2) | 16064.6 
16 15398 .6 (1409.6) | 16808.2 
17 16219.8 606.9 | 16826.7 
18 16340.6 606.5 | 16947.1 
19 15699 .2 803.5 | 16502.7 
20 | 14972.3 (1651.7) | 16624.0 
21 16716.2 607.3 | 17323.5 
22 16029.3 802.7 | 16832.0 
23 16130.5 (1409.7) | 17540.2 
24 16144.0 803.1 | 16947.1 
25 16164.2 (1409.9) |) 17574.1 
26 16431.4 802.7 | 17234.1 | 
27 16481.3 (1409.7) | 17891.0 
28 16520.9 802.6 | 17323.5 
29 | 15699.2 847.6 | 16546.8 
30 | 15787.2 847.3 | 16634.5 
31 | 15853.1 848.1 | 16701.2 


16298 .2 
16334.7 
16617.8 


18098 .7 
21260.2 
21599.5 
21751 .9 
21783.8 
22163.2 
23013.3 
23059 .9 
23069. 2 
23477.0 
24794 .8 


25675 .3 


25864 .2 


26077 .2 
27208 .3 


27242.1 
27779 .2 


27992 .3 
28201 .2 


Sighs Mo sh aS 


Ay 


846.2 


847.7 


846.1 


846.2 


846.4 


846.1 


846.1 


845.8 


846.8 


846.6 


846.7 


846.6 


845.9 


846.3 


78 


TABLE II (Continued). 


B 
A + 846.2 


16866. 1 
17145.9 


17863 .9 
18373.8 
18474.7 
22106 3 M 
22598.1 M 
23859 .7 
23906.0 M 
23915.3 M 
25640.6 
26522. 1 
26710.8 
28055 .0 
28063. 4 
1 


28088. 
28625. 1 


29047.5 


Ay 


803.1 


803.4 


(1651.1) 
(1651.2) 


802.5 
(1651.7) 
803.1 
(1649.3) 
802.7 
(1649.2) 
(1649.2) 
803.3 
803.1 
803.2 
(1649.8) 
(1650.0) 


(1649.9) 


(1649.3) 


(1649.2) 


(1649.7) 


(1649.7) 


(1649.8) 


Cc 
A | 1649.3 


17669.5 


17985.8 
18269.0 


19277.2 
19750.4 
22909 .4 
23248 .8 
23400 .8 
23433.0 
23812.4 
24663 .0 
24709.1 
24718.5 M 
25126.8 
26444.8 
26486.7 
27325 .2 
27448 .2 


Se Ese iSeRes 


= 


27513.5 
21527.2 
27126.4 


28891 .8 
29428 .9 
29518 .6 
29642.1 


Ay 


606.8 


(1409 6) 
(1410.4) 


607.0 


606.8 
606.8 
606.9 


606.8 
606.9 


607.2 
606.2 


606.8 
606.9 
606.7 


(1410.1) 
(1410.0) 


607.1 


606.8 


D 
A + 2256.1 


19273.5 
19784 .2 


23516.4 M 
23855.6 M 
24007.6 M 
24039.9 M 


25315.9 M 
25325.4 M 


27052.0 
27092 .9 


28055 .0 
28120.4 
28133.9 


29465 .1 
29473.4 


29498 .9 


30125.4 


79 


TABLE III. First Spark-Spectrum of Potassium. 


MS = Be | opted | 8% | i605] 2% | sp fone 
1] + 15165 |+ 844 | — 16009 +(2550)| + 17715 
2| 16340 4(1724)| + 18064 
3| 18286 (1692)| 19978 
4| 19778 (1682)| 21460 
5| 20230 | 849 | 21079 
6| 21758 | 848 | 22606 | s49 | 23455 | 846 24301 
7| 22195 | 847 | 23042 | 846 | 23888 | 849 24731 
g| 22384 | 945 | 23220 (1695)| 24924 
9| 22444 (2549)| 24993 

10 23337 | 848 | 24185 | 846 | 25031 

i 23665 (1694)| 25359 

12| 22909 | 850 | 23759 | 840 | 24599 | 864 | 25463 

13| 23204 2539 | 25743 

14 24102 (1708)| 25810 

15| 24429 | 852 | 25281 

16 26310 | 847 27157 

17} 24737 (1696)| 26433 

18 | 24845 (1701)| 26546 «| 847 27393 

19| 24882 | 844 | 25726 

20 | 24993 (1708)| 26701 

21| 25050 | 844 | 25804 | 850 | 26744 

22| 25171 (1695)| 26866 

23| 25210 (1694)| 26904 

24| 25485 (1707)| 27192 

25| 25779 | 945 | 26624 | @50 | 27474 | 847 28321 

26 | 26009 (1696)| 27705 

27 | 26187 (1691)| 27878 «| «847 | = 28725 

28 27570 | 849 | 28419 

29| 27192 (2540)| 29732 

30| 27246 (2541)| 29787 

31} 27636 (2550)| 30186 


80 


TABLE II! (Continued). 


Ne P a7 | = P4847 gag. «| =P F i605 ep Se > 542 
32) 28070 850 28920 850 29770 

33| 28458 (2552)| 31010 
34 29539 846 30385 845 31230 
35| 28725 | 848 | 29573 

36 | 28830 (2535)| 31365 
37| 29123 (2547)| 31670 
38 | 29371 (1693) 31064 

39| 29471 (1690)| 31161 

40 | 29638 (1704)| 31342 

41} 29888 844 30732 

42 30101 (2551)| 32652 
43 | 30499 (1703)| 32202 


1 << 847, 2 « 848, 3 « 847. From this ensues that Table III is not 
unequivocally determined, like II, because when e.g. only P and Q 
occur in a row, they can now equally well be placed in another 
row in the Q and Rk or R and S columns. 

it makes the impression that the number 847 = D hasa physical 
meaning, as also a value 846,2 occurs in the argon spectrum, which 
may possibly be a more accurate value for D. 


One more detail of the experiments deserves to be mentioned, 
In some cases the argon spectrum was observed in the potassium 
tube at the same time with the first spark spectrum of potassium. 
We have not to do here with a case of transmutation of potassium 
into argon, but with the penetration of atmospheric air, of which 
the argon has been finally left. When, however, all precautions are 
taken, the spark speetrum of potassium is emitted without argon lines. 


Mathematics. — “Explanation of some Interference-Curves of 
Uni-axial and Bi-axial Crystals by Superposition of Elliptic 
Pencils.” (Third paper.) By J. W.N. Le Hevx. (Communicated 
by Prof. Henprik DE VRiks.) 


(Communicated at the meeting of March 25, 1922) 


Some well-known interference-curves, fi. the hyperbola’s and the 
lemniseates are obtained by superposition of two equal unissons, 
under certain conditions, as was remarked in my first paper’). 

From this observation we may derive a parameter-equation for 
both cases, which enables us to construct the curves in a simple 
manner. 

The axes being at right angles, the unisson may be given by 

«=r cos2@ 
y =7 cos 2 (p 4- a). 

Each value of the phase-difference 2« corresponds to an ellipse; 
when we suppose, that this phase-difference increases each time 


with 2a —= —, the unisson has 7 ellipses. 


2n 
With regard to an easy construction, the angle 2y may also be 


supposed to increase with an 
UU 


The two equal unissons, pattially covering each other, are given by : 
J fo) « 


z=res2gp+a 

2 ad: (J) 
y =r cos 2 (Pp + a) + a} 
pene tat hs Sih lia Wa Gay 
y = ros 2(y' +a) —a\ 


where a is constant and <r. 
The distance between the centres is 2a p2. 


; mt : 
By altering 2@ (and also 2«’) from 0 to 3” the image of the hy- 
. . . 2 a > ° 
perbola’s is obtained, and from 5) to x, that of the lemniscates. 


1) These Proceedings Vol. XXIII, p. 1223—1225. 


82 


Each curve of the moiré-image corresponds to a certain constant 
difference (or sum) of phase. 

The equation will first be derived for a constant difference of 
phase 2a—2a’ = 206. 

This condition, together with (I) and (II) gives: 


«—a 
—— = cos 2p 
ifl 
«+a ( ) 
—— = 08 2 g' 
ip 
y—a . ‘ 
—___ == cos 2 p cos2a—sin2%psn2aa 
(Uv) 
yr . 
“____ = os 2(y'—6)cos 2 a—sin 2 (p'— GO) sin2a 
7 
Eliminating 2@ from (JV) by means of the relation 
sin? 2a + cos’ 20 = 1 
we get: 
ly is) ; Ke ya ; . 3 
/—__  — sin2 p | {eos 2@ —— cos 2 ~p — sn2@ 
| ie | Yr — 
Yi =p a | 9 ! ya u , t 
| —— — sin 2 (p'—0) ) cos 2 (g'—0) ae cos2(cp' — 6) — sin2 (p'—@) 
fs : 


or after reduction: 


cos? } 2 (p—g') + 26} — 2! a 008 2(p—q') +26} + 2 ere 20 (V) 
When in this equation cosg and cos’ are replaced, resp. by 
aw— wa ‘ , ele ; 
“—* and ei we get the equation of the moire-image in ay co- 
= a 
ordinates. 
It is, however, preferable to seek parameter equations. 
Suppose 2 (y—’) + 26 = 24, then (V) becomes: 
r? cos? 2 A — 2 (y*—a?) cos 2 A + 2(y?+a?)—r?7=0 .. (VI) 
which gives for y: 


y = + Vr" cos? A — a” \cotg? Av. 2 2 aaa 
The value of « follows from: ; 
om Dee O6=24 
cos 2 p cos 2 p' + sin 2 ~p sin 2 q' = cos 2 (A—@) 
or, with regard to (IIl) and after reduction: 
r? cos? 2 (A—O) — 2 (x? —a’) cos 2 (A—6) + 2 (#?+ a7) — r* = 0. 
This equation, being of the same form as (VI), we get for w: 


a = + Vr* cos? (A—6) — a? cotg* (A—6). 


83 


When the original angles gy, g’, « and «’ are again introduced, 
the parameter equations become: 


p) + (a—e')} —a? cota’ \(p— g') + (a—a' 

For a constant sum of phase, we find the same equations by 
changing v’ and a@’ into —q’ and — a’. 

In both cases, the image is the reflexion of the part in the first 
quadrant with regard to the axes. 

Characteristic is the function 


2 


T= ss i 7? cos? \(p 


Wagdas 
y 


SQ =V 2" cos? p — a? cota’ g. 


Bat (3 : a 
which is real for sin g > —. 
: 
sate eae! . : 
It has an initial value 0 for g = bg sin —, a fast reached maxi- 
A 


: a ‘ 5 : : 
mum for sin? ~= — and it becomes for this maximum —=7r—a. 
; r 


This is in accordance to the fact, that the circumscribed squares 
of the partially covering unissons have a common square with sides 
= 2(r—a), in which square the moiré-image is inscribed. 

For the more general case: 

z=r,cseag+ b =r, cos 2 gp’ — b 
y =r, cos2(p + a)+a y =r, cos 2 (p + a')—a 
we find: 


ee Vr? cos* (p—q') — b? cota’? (p—g') 


ie Vr? cos? \((p — g') + (a — a’) — a? cotg? }\(p — g') + (a—@)}. 


Construction of the Hyperbola’s. 

The construction is similiar to that, used for a Lissasous-curve, 
that is: straight lines are drawn parallel to the scaled axes of an 
orthogonal system and the points of intersection are joined diagonally. 

Fig. 1 shows a diagram of the funtion 


S@=V ” cos? g—a’ cotg? p 
for ~a=8, r=30. ¢ is given in units of $$— 32° and so, the 
unisson has **—12 ellipses. 
The maximum ordinate is r—a = 22; for g + 30° 


(f (80°) =V 483 while 22? — 484). 


The initial value of m= 15°, ae being = + ft. 
e 


Proceedings Royal Acad. Amsterdam. Vol. X XV. 


84 


Between toe initial and the maximum value of , there are but 
three ordinates and so, the scaled axes have three dividing-points 
and the image has three interference-curves, each consisting of four 
equal parts (Fig. 2). 

In the formula, y—y’ inereases from 15° to 30° and the phase- 
difference a—e«’ from —15° to +15°. 

The constructed curves may be compared to the experimental 
curves in fig. 8, obtained by superposition of two equal unissons, 


oa SO 


o— 
o” eS 
co 
~ 
) 
i = 
° ~o 
Lee 
° 
WS 
a 
2 
SS 
SS 
9. 
Ne 
SS 
a _ 
62 FY SF 6 7 (8 9, 140) N72 Wi) RS a oe eee 


Fig. 1. 


each containing 12 ellipses. A much finer result is obtained with 
unissons of f.i. 50 ellipses, or by comparing to constructed unissons 
in superposition — these drawings, however, require much time. 

It will be evident, that an image with more interference-curves 
may be obtained by interpolating a same wumber of curves between 
two succeeding curves of fig. 2. 


Construction of the Lemniseates. 

This construction is more difficult than that of the hyperbola’s, 
because the image, going to the centre, shows three different species 
of curves, viz.: ovals, flattened ovals and hyperbola’s with doubled 
ovals. ~ 

Only the outer curves are seen in the case of few isophasic lines ; 
they are as easily to construct as the hyperbola’s, viz.: by joining 
the points of intersection, but now following the other diagonal 
(fig. 4), according to a phase-difference, that begins with 90°. 

The constructed eurves of fig. 4 may be compared to the expe- 
rimental curves of fig. 5, the unissons having 12 ellipses each. 
lig. 5 is somewhat irregular, owing to the small number of ellipses. 

A new difficulty arises from observing, that the axes of co-ordi- 
nates are not axes of symmetry for the image of the lemniseates, 
as is required in the found formula. Still, this image was built in 


85 


some’ experiments, while another time, under apparently the same 
conditions, a family of ovals appeared. At last, it was found, that 
the angle between the planes of the pendulums caused the difference : 
the image of the lemniscates is not built, unless this angle differs 
from 90° and with a very large number of ellipses per unisson. 
So in fig. 6, where the angle between the directions of the two 
composing movements is + 145° and each unisson has + 120 ellipses. 

The reason for this large number of ellipses proceeds from the 
swift rising of the function in fig. 1. Dividing-points near the centre 
are not obtained, unless the interval 4—5 is divided into f.i. 15 
parts, corresponding to a phase-difference of ~° = 15/ and a number 
of 180 ellipses per unisson. 

The experimental number however is limited in consequence of 
the thickness of the ink-lines. 

The phaenomenon is mathematically explained as follows: 

The unisson 

= rcos 2Qp. 
y" =r cos 2(p + a) 
upon a system with angle 25, becomes upon an orthogonal system 
with the same bisectrix : 


a’ =r sin(8 + 45°) cos 2 mp + r cos (8 + 45°) cos 2 (p 4+ a) 
y =r cos (6 + 45°) cos 2 p + rsin (8 + 45°) cos 2(p + a) 


When 8 -+ 45° — y and seeking the equations of the moiré-image 
in a similiar manner as before, the composing (oblique) unissons are : 


(1X) 


“=r sin y cos2 p + 7 cos y cos2(p + a) +a 

y =P cos y cos 2 p + rsiny cos2(p + a) +a 
and 

«=rsiny cos 2q' + r cos y cos 2 (p' + a’) — a 

y =r cos y cos 2 y' + rsin y cos 2 (g' + a')— a 


and a point of the moiré-image has the parameter-equations: 


a sin Y —¥ cos y - ; = 2 7 
i Ep 7? (1 + sin 2 ¥) cos" (P—g') — a’ cotg* (P—’) 
cos Y — sin y 


x cos ¥ —y sin ¥ 


cosy — siny 


S==Vr? (1 + sin? y) cos? } (y—gq’) + (a—a'); — a? cotg? | (p—y') + (a—a’)} 
Now 


— 25 Ve cos* (p—gp') — a? cota? (¢ —¢’) 


y = £ Vr? cos? (p— ep) + (e—a)! — & cotg?} (p—e’) + (a—a’)} 
where 


6* 


86 


rrp 2.sin(y + 45°) 
is a moiré-image of two orthogonal unissons. 


The constant factor cos y—sin y only alters the magnitude. 


/ 
When 
x sin Y — y cos ¥ ith 
uz cosy — ysiny=y 
it follows, that 
y cosy — x siny sm y = 
Oe —— .(y cotg y—2z) 
cos 2 COSY Wah 
y siny — cosy sny = = 
SS SS (GSP BT 
cos 27 cos 2 
rie! sin y 
Omitting the constant factor ree that does not alter the form, 
os2y 


we find at last, that the moiré-image for oblique unissons proceeds 
from that for orthogonal unissons by the linear substitution 


i — a + y cotg y 

i —— y— a cotg y. 
The form, thus chosen, gives rise to an easy construction, exe- 
cuted in fig. 7. The new ordi- 
nate, f.i. is found by drawing 
from a point P (a, y) astraight 
line, that builds an angle = y 
with the ordinate of P. 

By this construction, the 
double symmetry is lost; the 
axes turn to each other over 
an angle 90°—y. 

In fig. 7, a flattened oval is 
obtained *); when the original 
curve lies nearer to the centre 


and turns its convex side to 
the axes, the hyperbola’s *) are built. 


1!) See the experimental curves in my first paper, fig. 4. 

3) A mathematical explanation of interference-curves, wholly different from the 
here given, is to be found in Mr. T. K. CoinmMAyANANDAM: On Haidinger’s Rings 
in Mica. Proc. Royal Society. Vol. XCV, p. 176—-189. 

The author maintains the pure hyperbola’s and the ovals of Cassini, which, 
however, build a rather rough approximation. 


J. W. N. LE HEUX: “Explanation of some Interference-Curves of Uni-axial and 
Bi-axial Crystals by Superposition of Elliptic Pencils’’. 


‘ 
4 


] 


Fig. 2. Fig. 3. 


vn 


Fig. 6. 
Proceedings Royal Acad. Amsterdam. Vol. XXV, 1922. 


SS Ee 


Bacteriology. — “Studies on ihe bacteriophagus of pv’ Herein.” I. 
By J. W. Janzen and L. K. Worrr. (Communicated by 
Prof. C. EykMman). 


(Communicated at the meeting of March 25, 1922). 
UW. The Bacteriophagus with regard to flagellates. 


We have been informed by pD’Hrreiie that the water of some 
Indian rivers possess the bacteriophagus properties. 

In connection with that we have considered it of importance to 
see how far flagellates out of a mixture of bacteria and bacterio- 
phagus also eat the latter. 

Ip order to do this we prepared a suspension of dead typhoid 
bacilli in saltsolution, and to a third part of this we added 2 cM‘ 
canalwater; a second portion was mixed with bacteriophagus and 
2eM* canalwater; a third portion was only mixed with the same 
quantity bacieriophagus as the second. 

After 9 days the two first portions had become considerably 
clearer and we could distinctly show flagellates in the microscopic 
preparation. 

Now dilutions were made, the number of bacteriophagus germs 
of which was stated in the wellknown way. 


We found: 
II emulsion + canalwater + bacteriophagus in 

1/400.000 cM* 71 islands. 
Ill emulsion + bacteriophagus in 1/400.000 eM* 380 islands. 


With another trial we found after 14 days: 
Il emulsion + canalwater + bacteriophagus in 
1/4000 mill. eM’ 120 islands. 

III emulsion + bacteriophagus in 1,400 mill. eM* 50 islands. 

This numbers are of the same range; the differences range within 
the mistakes of the experiments. 

The suspensions without canalwater remained absolutely turbid, 
because the bacteriophagus does not affect dead bacilli. 

From these two experiments we wish to conclude that the bacterio- 
phagus is not being affected by flagellates. 


88 


Ill. Constancy of the bacteriophagus properties. 


In our first communication we have proved that various bacterio- 
phagus strains behave differently with regard to different typhoid 
bacilli. 

Here follows a comparition of the bacteriophagus Sm in the sixth 
and tenth generation with regard to four different typhoid strains; 
the baeteriophagus was always fed with typhoid Sm. 


1. Clearing. 2. Checking. 3. Islandformation. 
6th generation | 10th generation 
Strains 1 2 3 | 1 2 3 
Wi = ++ - _ 4 ~ 
23 apse ar sear se stot ana gare 
24 = _ _ — -- 
25 Seay ee ee nen era ineniem| || cons sta” |) ar 7 


So here we see an absolute conformity. 

The behaviour of bacteriophagus Sm with regard to strain Wi is 
somewhat strange; in some generations we did not find any effect; 
in some others as above mentioned we did find shecking of the 
erowth in broth, but no islandformation. 

We have now observed whether the properties of the bacterio- 
phagus change when it is cultivated on different bacteriastrains. 

In the following. tabels the results are given in which 

I. Bacteriophagus Re direct from faeces, 


I]. a Re after having been fed with typhoidbacilli Sm, 
Ill. ed Wi direct from faeces, 

Le Gs Wi after having been fed with typhoidbacilli Wi, 
V. ss Wi after having been fed with typhoidbacilli Sin, 
VI. bE Sm after having been fed with ty phoidbacilli Sm. 


The thus obtained bacteriophagi were examined with regard to — 
5 typhoidstrains. : 

From this we see that the properties of the bacteriophagus do 
change when another bacillus has served as food in this sense, that 
no bacilli which used to affect are now left uninfluenced, but 
that an increase can appear in the number of strains which are 
influenced by the bacteriophagus; except for this strengthening 
however the bacteriophagus retains its specific properties, which in 
our opinion pleads more for a living being than for a ferment. 


1. Clearing. 


89 


2. Checking. 


3. Islandformation. 


Re after having been 


I Bact. Re direct from faeces. | I Bach d typhoidbacilli Sm. 
Typhoid 
ole clea ie 
Wi = = _ as = cau 
1 — f+ | tE = +4+4++ | 444+ 
24 - - - ~ 444+ 
27 — — — — “= ~- 
29 = = = tobe | seek gp ete: 
Ill Bact. Wi. direct from faeces. | SEEAGHIL Asaicdeect as 
Typhoid 
7 2 mines , 3 
Wi | ttt | 44+ | ttt | 4444+ | H+ | 4444+ 
1 as = = = = a 
24 — ++ | +4+++] —- ++ | ++++ 
27 - + |4++++] - + +444 
29 = fee ft | | HH | 44+ 


V Bact. Wi after having been fed 


with typhoidbacilli Sm. 


VI Bact. Sm after having been 
fed with typhoidbacilli Sm. 


Typhoid 
strains 


Wi 
1 


1 2 3 | 1 2 3 
tanta gies |) sett ~ = = 
itera St | = Foes ||, tela ee 

re sae | state be = = = 

= a: “Lp asl = = = 
shat Steg be teat |iectestes aly > ; i 
Lab. for hyg. of the University. 


Amsterdam, March 1922. 


Physics. — G. Hertz: “On the Mean Free Path of Slow Electrons 


in Neon and Argon.’ (Communicated by Prof. P. Karenrust). 
| A 
(Communicated at the meeting of March 25, 1922). 


The reason for undertaking these measurements was given by 
researches concerning the efficiency of non-elastic impacts of electrons 
in neon and argon at potentials just above the excitation-potential. 
It is known, that those collisions between electrons and the atoms 
of rare gases, which take place below the excitation-potential 
characteristic for each gas follow the laws of elastie collisions. As 
soon as the kinetic energy of an electron surpasses the value 
corresponding to the excitation potential, it can, on collision with 
an atom, transfer energy to the latter and thereby raise it from its 
normal state to a higher quantum-state. This, however, does not take 
place at every collision between a sufficiently fast electron and an 
atom; only a certain part, in the case of rare gases most probably 
only a small fraction, of these collisions is non-elastic and causes 
excitation of the colliding atom. This fraction we call the efficiency 
of the particular non-elasti¢ impact. It is equal to the probability 
that an impact of an electron possessing the required energy really 
leads to a transfer of energy. It is naturally a function of the 
velocity of the electron. The form of this function however is not 
vet known. 

In a glow-discharge the two rare gases neon and argon show a 
characteristically different behaviour, which among other things 
manifests itself under similar circumstances by producing in neon 
a much more intensive emission of light than in argon. The reason 
for this different behaviour according to G. Horst and E. Oosrrruuts ') 
probably lies in the fact, that in argon electrons having a velocity 
above the excitation-potential readily transfer their kinetic energy 
to the argon-atoms thereby exciting the emission of ultraviolet rays 
(resonance), while in neon only a small fraction of the impacts leads 


*) G. Housr and G. Oosreruuts, Physica. 1, 78, 1921. 


SIH 


to radiation the majority of the electrons only imparting their energy 
to the neon-atoms after falling through a potential-difference equal 
to the ionization-potential, thus causing ionization. 

In consequence one would expect a great difference in the effi- 
ciency of the first non-elastic impact in neon and argon. Preliminary 
experiments concerning the relative value of the efficiency in these 
gases however have shown, that this difference is not large enough 
to explain the different behaviour. So there must be another reason. 
Beside the excitation-potential and the efficiency there is only one 
quantity which determines the number of the non-elastic impacts, 
and that is the mean free path of the electrons. Up to now it was 
assumed, that the value derived from the kinetic theory of gases 
for particles of infinitesimal small dimensions and large velocity, 
viz. 4)’2 times the mean free path of a gas-molecule, should hold for 
the electrons. Recently however, H. F. Mayer) and C. Ramsaver *) 
have found, from the measurement of the mean free path of electrons, 
that also for slow moving electrons this quantity depends on the 
velocity of the electrons, this dependence being different for different 
gases. Especially between neon and argon Ramsaurr found a very 
marked difference. While in neon the mean free path depends only toa 
slight degree on the velocity of the electrons and is nearly equal to 
the value of the kinetic theory, argon shows for very slow moving 
electrons, below 1 volt anomalously large values of the mean free 
path. The mean free path then decreases and becomes a minimum 
at approx. 12 volts, the minimum being about one third of the value 
of the kinetic theory. This fact must be of importance for the pheno- 
mena produced by electrons passing through a gas, especially in the 
case of argon, where the mean free path has its minimum value 
at a potential nearly equal to the excitation potential. 

Considering the great importance of the dependence of the mean 
free path on the velocity, not only for the understanding of the 
action of electrons in gases, but also for the theory of the atom, it 
appeared desirable to me, to verify this dependence by direct ex- 
periments, in order to obtain accurate values for the ratio of the 
mean free paths in neon and argon, this ratio being of importance 
for the evaluation of comparative measurements in the two gases. 
The applied method is based on the following idea: If in an appa- 
ratus of given geometrical dimensions electrons of a certain velocity 
are allowed to move in a rare gas in a space, in which there is 


1) H. F. Mayer, Ann. d. Phys. 64, 451, 1921. 
*) C. Ramsaver, Physik. Zeitschr. 22, 613, 1921. 


92 


no electric field, the mean free path alone will determine their 
movement and distribution, so long as the velocity of the electrons 
is not larger than that corresponding to the excitation potential, 
that is: so long as the impacts are entirely elastic. If the apparatus 
is then filled suecessively with different rare gases, the movement 
of the electrons in the one gas must be the same as that in the 
other, provided the pressures are chosen in such a way that the 
mean free path is the same. If, on the contrary, the pressures 
of both gases has been adjusted so as to make the movement of 
the electrons the same, the inverse ratio of the corresponding 
pressures will give the required ratio of the mean free paths under 
equal pressure. This ratio must be found to be independent of the 
pressure used in the experiments. 

The apparatus used is shown in fig. 1. G is a 
tungsten filament, MW, and N, are grids P is a 
receiving plate, and H is a metal shield whieh 
prevents electrons from coming from G to P by 
any Other way, than through the space between 
the two grids. All metal parts were made of copper. 
Before mounting the apparatus they were treated 
with nitric acid and showed a clean metallic surface 
after the tube had been exhausted during 5 hours 
at 400°. The gases used were so pure that no 
non-elastic impacts, below the excitation potential 
could be detected even by a very sensitive device. 

3efore the final measurements, preliminary mea- 
surements were made with a simpler device, which 
differed from that of fig. 1 by omission of the grid N,. 
Though the experiments made in this way do not 


allow an accurate quantitative evaluation, the results 
are given here briefly, as they show very simply and clearly 
the different behaviour of neon and argon. During these prelimi- 
nary measurements the entire apparatus was al earth-potential, 
except the filament which was brought at a variable negative 
potential, so as to produce an accelerating electric field between 
filament and grid. The electron-current passing on to the receiving 
plate P was measured by a galvanometer. The measurement consisted 
simply in noting the current as a function of the accelerating 
potential between G and N,, in neon and argon under various 
pressures. In order to be independent of slow variations of the 
current in the filament, a second galvanometer registered the total 
electron current, and the quotient of the plate-current and the total 


93 


9 4 6 T= 6 20 Volk. 


) 4 i) 42 16 20 Volt 


94 


electron current from the filament was calculated. As the tempe- 
rature of the filament was always low, this quotient was independent 
of the intensity of the electron emission of the filament. 

This quotient, multiplied by a constant is plotted in the curves of 
the figs 2 and 3 for a series of pressures in neon and argon as a 
function of the potential difference between Gand V,. The numbers 
near the curves show the gas pressure in m.m. mercury. We see 
immediately the extra-ordinary difference in the behaviour of both 
gases. While in neon an increase of pressure for all velocities 
reduces the plate-current in about the same degree, argon shows at 
10 volts a remarkable decrease of current at pressures, where at 
1 volt practically no influence is observed. As the observed decrease 
of current can result only from the collisions between the electrons 
and the atoms of the gas, we can deduce from these measurements 
qualitatively, that the mean free path of electrons in argon varies 
strongly with the velocity of the electrons, while in neon this is 
not the case, or at any rate only to a small degree. A quantitative 
calculation in the sense of the above consideration can only be 
taken from these measurings for slow electrons up to about 10 volts; 
at higher velocities the electrons produce secondary electron emission 
from the metalwalls. To retain these secondary electrons, the second 
grid N, was introduced a retarding potential equal to */, of the 
accelerating potential between G and NV, being applied between 
N, and P. The result of such series of measurements is shown in 
figs. 4 and 5 wherein the numbers near the curves again show 


Oo O Vecuum 


| 
| 
| 
i) 4 6 12 fn 16 29 Volt 


95 


the gaspressure in millimetres mercury. For the evaluation of 
these measurements the distribution of the electron velocities was 
first measured in vacuo by means of a variable retarding field with 
the result, that, in consequence of the initial velocity of the electrons, 
the potential gradient at the filament and the Volta-potential difference 


0 4 8B Tae Gen 20 Volt. 


between filament and grid, 0.7 volt had to be added to the applied 
accelerating potential, in order to obtain the true velocity of the 
electrons. For a series of electron velocities the logarithm of the 
plate-current was registered as a function of the pressure in neon 
and argon. A similar character of the curves in neon and argon 
is to be expected, assuming that the method is correct, in such a way 
that for each velocity the proportion of corresponding pressures in 
neon and argon (i.e. pressures giving equal plate-currents) is constant. 
This is in fact the case for all electron-velocities up to 16 volts. To 
show this, the curves so obtained for a number of velocities are 
reproduced in fig. 6. The evaluation is simplified by the fact that 
the first part of the curves is straight. From the slope of these 
straight portions we ean obtain directly the ratio of the corresponding 
pressures and so also the ratio of the mean free paths of the 
electrons. 

A condition for the correctness of the method here applied is, that 
all collisions between electrons and atoms are absolutely elastic. By 
reason of the very low efficiency of the non-elastic impacts below the 
ionization potential in the rare gases this is no doubt the case for 


96 


potentials between the excitation- and the ionization-potential and for 
the low pressures used here. Things are different above approx.16 volts, 
the ionization potential of argon. This already can be observed at 
the curves for argon at higher pressures in fig. 5, by a bend in 
the curves at 16 volts; consequently the ratio of corresponding 
pressures is no more accurately constant there, as is to be seen in 
fig. 6 at the curves for 18 volt. At the same time this curve shows, 


06 


04 


9 002 004 006% 0 Q02 006 006 "Yn 


06 -— ~ 06 
42 Volk. 


18 Volk . 


04 


04 


02 


ore op2 oe 006%, oO 
Fig. 6. 


that for the lower pressures the number of ionising impaets is so 
small as to play no part, so that there is no objection against 
deducing the ratio of the mean free paths from the ratio of the 
slopes of the first straight parts of the curves. 

As a result of the measurement, the values for the ratio of the 
mean free paths of electrons in neon and argon obtained in this 
way are shown in fig. 7 as a funetion of the potential corresponding 
to the velocity of the electrons; in fig. 8 they are plotted as a 
function of the root of this potential, being proportional with the 


OG 


velocity of the electrons. The dotted line in fig. 8 shows ‘for comp- 
arison the values of this ratio as deduced from Ramsavpr’s measure- 
ments. It will be seen that our measurements verify not only the 
fact of the variation of the mean free path of the electrons with 
their velocity, as found by Ramsauer, but also the general character 
of this variation. The maximum of the curves was found in the 
present measurements at a potential about 2 volts less than in 
RAMSAUERS. 

The action of the slowest electrons is theoretically of special interest. 
~As however the accuracy of such measurings decreases for ex- 
tremely slow electrons an extrapolation in the direction of the 


= | ME semipetemi sf |S 
sss “ Ar | 


9 5 10 15 20 \ 


Fig. 7. 


velocity zero is always doubtful. If we stipulate, according to the 
results of Ramsaver that the electrons in neon show nearly normal 
values of the mean free path, it appears that, according to the here 
obtained results, the mean free path of electrons in argon on 
approaching zero-velocity, do not reach an infinite value, but one 
about 3 times that calculated from the kinetic theory for very 
rapidly moving particles of infinitesimal small dimensions. This figure 
can however, by no means lay claim {(o accuracy. 

The number of collisions of an electron passing through a unit 
length under the influence of an electric field /, in a gas, in which 


: hee Op 
its mean free path is 4, is —— —, that is, inversely proportional 
6 4 
Wipe 
m 


of the square of the mean free path. In argon the mean free path, just 
below 12 volts, the excitation potential, reaches its minimum of about 
1/, of the value derived from the kinetic theory. We can therefore 
conclude that an electron of this velocity in argon in passing 


98 


through a length unit makes about 9 times as many collisions as 
would be expected from the kinetic theory, while in neon the 
number of collisions is nearly normal. This shows clearly, why 
in argon non-elastic impacts above the excitation potential have a 
marked effect, while under similar conditions in neon they are 
hardly noticeable. 


Kindhoven, Laboratory of the 
Philips Incandescent Lamp Works. 


Anatomy. — “On the morphology of the testis of Rana fusca Résel” 
By G. J. van Oorpr. (Communicated by Prof. J. Bore.) 


(Communicated at the meeting of April 29, 1922.) 


Introduction. 

In recent years several investigations have given us a better 
insight into the course and the structure of the seminiferous tubules 
of a number of Mammals and of one Bird (cock). Formerly it was 
tried to isolate these tubules by the process of maceration and teasing 
in order to establish their form, their mutual relation and their con- 
nection with the rete testis. The results were not convincing, however, 
because it could not be traced with certainty whether the free ends 
found were natural or had originated by tearing. 

By means of complete series of sections and wax-reconstructions 
Bremer (1911) succeeded in disclosing the complicated structure of 
the embryonic human testis. He discovered that the testis tubules 
form a closed network. Employing a new, good injection method, 
followed by maceration and teasing, Huser and Curtis (1913) isolated 
in the testis of the adult rabbit several arch-shaped seminiferous 
tubules, connected to the rete testis with both extremities. Besides 
these simple “single-arched” (n-like) tubules, ““double-arched” (m-like) 
tubules, connected with the three free ends to the rete, were met 
with. Relatively simple tubules as well as canal-systems of compli- 
cated structure were found in the rabbit’s testis; canals terminating 
in blind ends or diverticula were not described, however. Applying 
the same method Hupur (1916) discovered in the testis of the cock 
that the seminiferous tubules form a network, in which no blind 
ends occur. 

Studying complete series of sections Curtis (1913) met with 
various single-arched tubules in the testis of the mouse. Anastomoses 
between two arches occur but rarily. Later on (1918) Curtis inves- 
tigated the testes of mouse, rabbit and dog and in these animals he 
also found the simple n-like tubule to be the original one. However, 
the testis of the mouse shows the simplest structure, then the testis 
of the dog and next that of the rabbit follows as to complication. 

Independent of Curtis , pk Burter and pe Ruirer (1920) came to 
the same results in studying a number of complete series of sections 


nr 
‘ 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


100 


of testes of mouse-embryos of 9—17 mm. length. The fundamental 
form of the embryonic testis tubule is a simple n-like tube, of which 
the convex side is directed towards the periphery and of which the 
extremities are connected with the future rete testis. A number of 
these tubes are placed serially behind each other; anastomoses between 
the arches and double-arehed, m-like tubes oecur also. The plane of 
the arch is perpendicular to the longitudinal axis of the testis. 
Tubules, terminating in blind ends, were rarely found. In the caudal 
part of the testes of embryos of 18 mm. and smaller a so-called 
,canal-complex” occurs, from which later on — for in older testes 
more arches are to be found than in younger ones -— additional 
arches probably develop. The tubules number from 10 to 13 in the 
mouse. After the ,,canal-complex”’ has disappeared, the longitudinal 
growth of the testis-tubules sets in and then the tubules begin to coil 
strongly. From the longitudinal stem, originally epithelial, the rete 
testis develops. 

In a second paper De Burner (1921) traced the morphology of a few 
Marsupialian testes (Perameles obesula, Didelphys spec., Halnaturus 
Bennett). The single-arched tubule was found again; in Perameles 
the testis (embryo of 50 mm.) is still more simply built than in the 
mouse; the testis of Didelphys (embryo of 20 mm.) is composed of 
two long, strongly twisted tubules. These tubules are very numerous 
in’ Halmaturus (embryo of 105 mm.), where they vary from 200 
to 300. 


Starting from the above investigations it was but natural to trace 
in one of the representatives of the other Vertebrate groups, how 
the shape of the adult seminiferous tubule derives from the embryonic 
one. After consulting Dr. H. M. pe Bertier, to whom I wish to 
express my thanks for his interest in this work, I chose the co m- 
mon Frog, Rana fusca Rosel. As it appeared during the investi- 
gation that in immature frogs the course of the vasa efferentia, 
the duets through which later on the spermatozoa pass to the kidney, 
show different peculiarities, | decided to communicate simultaneously 
a few remarks concerning the course of these channels in immature 
frogs in the beginning of their second year. 


Material and methods. 

All specimens of the common frog were caught at Bilthoven 
(near Utrecht) in Sept. 1920. The smallest, immature frogs measured 
2.8 em. (from the head to the rump), the largest, adult spec. 6.3 em. 
According to GAupp (1904, IIl, pp. 298—800) frogs measuring cire. 


LOL 


30 mm. are in their second, those measuring cire. 50 mm. in their 
third year, whilst they become mature in the end of the fourth year. 
The gonads of the immature frogs were taken from the body, 
together with the kidney; they were fixed in Bouin’s solution and 
after 5 days they were transferred to ale. 90°/,. Subsequently the 
testes were cut — mostly frontally, but in a few cases transversely 
— into complete series of sections of 10m. The sections were 
generally stained with Dertarizib’s hematoxylin and van Gikson’s 
solution, sometimes eosin or nigrosin was used instead of van Girson’s 
solution. Especially with van Gigson’s solution the connective tissue 
between the seminiferous tubules assumes a deep red colour. 

From the testes of the adult frogs only the middle part was 
sectioned, from all other testes complete series of sections were made. 
As far as necessary, the sections were drawn on transparent paper 
at a magnification of 100, with the aid of the large projection- 
apparatus of Zxiss.') By laying these transparent papers on each 
other, it is generally not difficult to trace the course of the tubules, 
which are cut transversely. Originally 1 had the intention to project 
on a certain plane several tubules, passing over into the rete testis 
with a common stem, but in many cases this method proved not 
practicable, especially in adult testes, as here the tubules are too 
close to each other and too much twisted. Fig. 10 is even so 
schematized that only the mutual relations of the tubules, drawn in 
one plane, are shown. In order to get an exact insight into the 
course of the seminiferous tubules a few sections of the part of the 
testis, in which these tubules occur, are also reproduced. 

In the following the development and structure of the testis tubules 
are described in the first place and further the particular course of 
the vasa efferentia in six immature testes is treated. 


The development and structure of the seminiferous 


tubules. 


An extensive literature deals with the development of the gonads of 
frog-embryos. As most of these investigations do not bear upon my 
subject, I will only communicate the results of Wrrscui, who in his 
,Experimentelle Untersuchungen iiber die Entwicklungsgescliichte 
der Keimdriisen von Rana temporaria” (1914) not only traced the 
different developmental stages of the gonad, but also drew attention 


1) 1 have to thank Prof. A. J. P. van pen Broek, whose kindness enabled me 
to use the apparatus of the Anatomical Institution of the University at Utrecht. 


7* 


102 


io the morphology of the testis tubules of newly metamorphosed frogs. 

After describing the development of the so-called indifferent gonad 
— which possesses a germinal epithelium consisting of one layer 
and surrounding a central lumen, the 
primary genital space, in which cell-strands, 
the sexual strands, situated at regular 
distances behind each other, have origin- 
ated from the mesonephros — Whirscat 
traces the development of the ovary and 
the direct testis-development. The indirect 
testis-development, which takes place in 
the so-called hermaphrodites of 
Priicrer is elaborately described; in this 
case the testis originates from an ovarium- 
like gonad’). As this development does 
not bear directly upon my subject and 
as the final stage of both direct and 
indirect testis-development is the same, 
[ will not enter any further upon this 
question. Shortly, the direct testis-develop- 
ment is as follows. The germ cells leave 


Fig. 1. 


Schematized longitudinal 


section of the testis of anewly the germinal epithelium, wander through 
metamorphosed frog. After the primary genital space and settle on 
Witscut (1914). the sexual strands. All germ cells leave 
the germinal epithelium about simultaneously, so that only the 
peritoneum remains. Between the germ cells and the compact core 
of the sexual strands several slits originate: the anlages of the 
lumina of the ftestis-ampullae. Then the ampullae differentiate from 
each other 4nd in this way the anlages of the testis tubules develop. 
These ampullae are short, almost globular tubules, with a lumen 
disappearing later on. 

The convex side of the ampullae is directed towards the periphery 
of the testis; with the other side they are attached to the central 
strand. The sexual strands are connected with the mesonephros. The 
distal ends of these strands thicken, fuse and in this way the central 
strand originates in the longitudinal axis of the juvenile testis. After 
some time the inner-testicular network or rete testis originates from 
the central strand, as well as the vasa efferentia from the compact 
sexual strands. 

A schematized longitudinal section of the testis of a newly meta- 


!) Wirscut’s latest publication (1921) treats the same subject. 


103 


morphosed frog is reproduced in fig. 1, which is drawn after Wirscut 
(@9114; fig. A; p. 21.) 

In the literature, dealing with the further development of the testis, 
only some scattered remarks on the testis tnbules are to be found. 
“Damit (i.e. when the stage, reproduced in fig. 1 is reached) haben 
die Samenkandlchen im wesentlichen ihren definitiven Zustand erreicht” 
(Witscar 1914, p. 20). Then the testis ampullae grow out “zu 
den bekannten schlauchf6rmigen und gewundenen Samenkanilehen, 
wahrend sich die Keimzellen ziemlich rasch vermelren’ (WitscHi 
1914, p. 20). However, nothing is mentioned about this outgrowth 
and about the question whether the tubules are connected with each 
other. 

Gaurp deseribes the form of the testis tubules of the adult frog 
as follows (1904, III, p. 307): “Sie beginnen an der Oberflache 
gerade und mit radiirer Anordnung gegen das Centrum hin, laufen 
dagegen mehr central vielfach gewunden durch einander. Die radidren 
Canalabsehnitte der peripheren Zone beginnen blind unter der Tunica 
albuginea, und haufig sieht man hier, wie zwei gesondert entstehende 
sich mehr central mit einander vereinigen”’. 

It is my intention to trace how the structure of the adult testis 
originates from the simple one of newly metamorphosed frogs, the 
latter having been described by Whirscut. 

I started with the study of testes of frogs in the beginning of 
the second year. It proved easiest to get an insight into the form 
of the testis tubules by studying frontal testis-sections, in which a 
great number of transversely cut tubules are visible (ef. figs. 2, 3, 
6, 7, 8, 9). These sections were drawn on transparent paper and 
then compared. 

In figeg. 2 and 3 parts of two frontal sections of the right testis 
(long 1.8, broad 1 mm.) of a com- 
mon frog with a head-rump length 
of 3.5 ¢.m. are reproduced. Fig. 2 
is a section close to the rete; 
many tubules transversely cut, 
are distinctly visible. On tracing 
the course of the three tubules, 


designated A, #& and C;, to the 


Fig. 2. periphery, we observe that in most 
Section of the testis of a juvenile Cases these tubules branch, like 
frog (beginning of second year), near the fingers of a hand, into anumber 
the rete testis (< 100). of tubules (fig. 3, which is drawn 


after a section close to the periphery) and that all these tubules are 


104 


terminating in blind ends, Tubale A ramifies into five tubules (4 J, 
All...AV), B into two tubules (BJ, BIJ), while C remains 

EN ; single. Already in fig. 2 it is visible 
( that the tubules A and £& divide 
into a certain number of branches, 
for these tubules are designated 
Al—V and B/—/T7 in this figure. 
On comparing figs. 2 and 3 we see 
that the space between the tubules, 
the interstitium, is larger near to 
the rete than towards the periphery. 
As has already been mentioned, fig. 3 


is drawn after a section close to the 


Fig. 3. testis-surface, so that not all testis 
Section as in fig. 2, but more tubules are cut transversely. Many 
near the periphery (< 100). tubules, which were not cross-cut, 


were indistinctly visible and for this reason this part of the section 
is shaded by oblique lines. 

To elucidate the course of the seminiferous tubules, I have projected 
the circumferences of the testis tubules A, B and C' on a sagittal 
plane of the testis (this plane is marked by a —.—.— line in 
fig. 3). This is reproduced in fig. 4, in which the course of these 
tubules can be seen. Moreover it is visible that the duets of the 
rete into which the tubules A, ArAvAu BI Ay BI C 
5 and C’' pass over, are directly Fig 3 x 


v ‘ 


connected with each other. 
The left testis of the same 
frog was cut transversely. The 
testis tubules are built in the 
same manner as those of the Fistor 
right testis. However, on com- d 
paring the form of the tubules 
of the cranial and caudal part 
of the left testis with the form Fig. 4: 
of the tubules of the middle projection of the tubules (designated 
part of the right testis, we see in figs. 2 and 3) on a sagittal testis- 
that in the former the number Plane (< 150). 
of simple, not branching tubules is much larger than in the latter. 
A peculiarity of this left testis is that the most caudal vas efferens 
is not connected with the rete testis. In this testis there is a small 
caudal part, consisting only of three testis tubules, which do not 
open into the rete, but are directly connected with the mesonephros 


105 


by an efferent duet. In fig. 5 this is figured. Only these caudal vasa 
efferentia are projected on the mid-sagittal plane of the testis. Moreover, 
two-single testis tubules, directly 
passing over into the rete testis, 
are sketched; the vas efferens, 
previous to the last, gives off a 
side branch to the last efferent 
duet, but a connection is not 
established, however. 


Two frontal sections of the left 
testis (long 6, broad 3,5 m.m.) of 
a frog in the beginning of the third 
year (4,75 ¢.m. in length) are 
reproduced. Fig. 6 shows a section, 
close to the rete testis, of which 
different parts are visible. The 
tubules A, B, C and D are sepa- 
rately connected with the rete; 
tubule B just ends in the rete in 
the section reproduced ; in a neigh- 
bouring section tubule C is con- Fig. 5: 
nected with this same rete canal. 


Projection of the two posterior vasa 
In this figure arrows indicate with efferentia on the sagittal longitudinal 
which part of the rete a few of testis-plane. Frog from the beginning 
the testis tubules are connected. of the second year (< 100). 

When we trace the course of the testis tubules, indicated A, B, C 
and D towards the periphery, we see that here also these tubules 
divide into many others; e.g. tubule A splits up into seven, B into 
five, C into four and D into six others. Fig. 7 shows a section of 
the same testis about halfway the periphery. At this level tubule A 
has divided into 3 branches (A /—//, A I/I-—V, A V/I—V1/1), B 
into three (6 V, branched off nearer to the rete is very short), D 
into four, while tubule C has not divided as yet; this will take 
place closer to the periphery. The space between the tubules, being 
rather wide near the rete, is very narrow at this level. Most tubules 
end near the periphery ; anastomoses are never found. 

On comparing the testis of a newly metamorphosed frog (tig. 1) 
with that of a second or third-year one (figs. 2—7), we find that the 
testis tubules, which are single originally and terminate in blind ends, 
divide already in the second year into a number of branches (like 
the fingers of a hand) and that this subdivision has increased in the 


106 


third year. The testis having strongly increased in size during this 
time, it is impossible that several testis-ampullae have fused to form 
such acanal system. On the 
contrary, we must conelude 
from the stages, described 
above, that the testis tubules, 
which are originally simple 
and very short and whieh 
are called testis ampullae 
then, divide toward the 
periphery into a number 
of tubules and that these 
branches are connected with 
the rete by the proximal 
part of the ampulla. On 


Fig. 6. comparing the different sec- 
Section of the testis of a frog of the third tons") we see that both 
year; the rete is partly visible (< 50). length and diameter of the 


seminiferous tubules have strongly increased. 

Turning now to the testis of the adult frog, we observe almost the 
same here. In figs. 8 and 9 parts of two frontal sections of the left 
testis (long 10.5, broad 7 mm.) of ~ 
an adult common frog (length 
6.3. em.) are reproduced. The 
tracing of the course of the strongly 
ramified testis tubules and the 
graphic reconstruction of this taking 
too much time, I ean only des- 
cribe a few tubules, not very 
strongly branched. They are 


reproduced in figs. 8 and 9anda 


reconstruction of the same tubules, 


beside each other and in one Fig. 7. 
plane is given in fig. 10. Thishad Section as in fig. 6, but about half, 
to be done, because the tubules, way the periphery (x50). 
winding too much around each other, especially in the neighbour- 
hood of the rete, could not be reproduced, projected on a certain 
plane. 
The tubules, designated AJ and A/J// in fig. 8 do not branch 
1) Originally { had the intention to reproduce all the figures at the same magni- 


fication (> 100); this proved impossible, however, the figures of immature frog- 
testes then becoming too small and those of adult frog-testes becoming too large. 


107 


further towards the periphery; tubule B /—J/ (fig. 8) splits up 
into two tubules towards the periphery (fig. 9), while B /// is very 


Fig. 9. Section of the testis of an adult frog, near the periphery (« 50). 


short and ends blindly about halfway the periphery (fig. 10). If the 
testis had developed further, this short tubule would probably have 
grown peripherally. Tubule C divides into 5 parts. A, 6 and Care 
connected with the rete close to each other. 

On comparing this testis with those, described above, we see that 
apart from the size, there is no fundamental difference in the shape 
of the tubules. The seminiferous tubules of the adult testis have the 
same shape, but are longer and thicker. They form no anastomoses 
and all end blindly. Most of them are strongly branched. The 
tubules twist, especially near to the rete. Towards the periphery 
the tubules are situated so close to each other that there is but a 


108 


very narrow space lett for the interstitium. Towards the rete testis 
this space increases in width (ef. figs. 9 and 8). 


Fig. 10. Schema of the course of the testis-tubules, designated 
in figs. 8 en 9 (50). 


The course of the vasa efferentia in frogs 
in the beginning of the second year. 


It is generally known that in adult frogs the vasa efferentia, 
which arise at the medial side of the testis, form a network, the 
extratesticular network, between testis and kidney. The number 
of these channels greatly varies. According to Gaupp (1904, III, 
p. 355) they number from 4 to 11 in Rana fusca. These differences 
are not only individual, but occur also in the right and left testis 
of one and the same animal. Channels which terminate blindly and 
do not reach the kidney are numerous, according to Gaupp. 

Investigating a number of testes of immature frogs, I found that 
here these particuliarities were also present. A conspicuous differ- 
ence is that the extratesticular network has not developed as well 
as in adult frogs, the vasa efferentia being still situated serially 
close behind each other in the mesorechium. 

I will describe six testes, derived from two frogs of 2.8 em. and 
one frog of 3 em. in length. With regard to the vasa efferentia, 


109 


they show the following particuliarities and differences, sketched 
schematically in fig. 11 a—/; testes, corpora adiposa and kidney 
are dotted, while rete testis and vasa efferentia are black. For sim- 
plicity’s sake all the ducts are indicated by successive numbers. 

Fig. 11a gives a schema of the right testis of a frog, measuring 
2.8 cm. in length. From the testis to the mesonephros 4 efferent 
ducts run, of which the two last have fused over some distance. 
At the cranial side of the testis there is also a vas efferens (N°. 2), 
but this one is not connected with the mesonephros. It runs cranial- 
ward and ends in the fat body. Still more in front of the fat 
body there is a very short vas efferens, connected neither with the 
testis nor with the kidney. 

In fig. 115 a schema of the left testis of the same juvenile frog, 
with 10 efferent ducts is reproduced. The most cranial one, running 
only over a short distance in the fat body, can be compared to the 
first vas efferens of the right testis of the same frog. The rete testis 
is connected by 8 different vasa efferentia (N°s 2—9) with the 
mesonephros. N°s 5 and 6 arise from the rete at some distance from 
each other, but quite near to the testis-surface they come close 
together and run parallel without fusing, however, to the mesone- 
phros. The two ducts (N°s 8 and 9) at the caudal side of the testis 
arise close to each other but separately, from the testis, and unite 
just outside the testis to form a common duct. As is the case in 
the testis described above (p. 8) and sketched in fig. 5, the 10" vas 
efferens is not connected with the rete testis. Only a few semini- 
ferous tubules open into this duct; so these are directly connected 
with the kidney. 

The two testes sketched in fig. 11¢ and 11d belonged to a frog, 
also measuring 2.8 cm. in length. In both the most cranial efferent 
ducts have no direct connection with the mesonephros, but run 
cranialward to the fat-body and from here to the kidney. In the 
right testis, behind this efferent duct, there are still six others, from 
which Nes 3 and 4 are only separated over a short distance, quite 
near to the kidney. 

In the left testis of the same animal the 2¢ and 3" vasa efferentia 
arise separately from the rete; they fuse near the mesonephros to 
form a common duct. The caudal vasa efferentia, Nes 5 and 6, run 
parallel in the testis and unite there, where they leave the testis; 
then they split, subsequently they again form one duct and finally 
they enter the kidney separately. 

The right testis of the specimen, the last to be described (3 em. 
in length), shows only one peculiarity (fig. 11e) ie. the 3°¢ and 4 


110 


Fig. 11. Schemata of the course of the efferent ducts in 
6 testes of juvenile frogs. 


111 


vasa efferentia, running close to each other, fuse near the kidney. 

The left testis is remarkable for the following facts (fig. 11/). 
The most cranial vas efferens runs like the most cranial ones, sketched 
in fig. 11a and 116; the third vas efferens runs like both cranial 
efferent duets of fig. 11¢ and 11d and moreover, a short side-duct 
(N°. 2), coming from the fatbody, opens into it. The vasa efferentia 
Nes 5 and 6 are close to each other, especially outside the testis, 
but enter the mesonephros separately. The 7'" and 8" vasa efferentia 
leave the rete testis united and split outside it; the 9' vas efferens 
finally is connected with the kidney, but does not reach the testis. 

So we have seen that the course of the efferent ducts in immature 
frogs is as variable as in adult ones and that there is no symmetry 
between left and right testis of the same animal. 


SUMMARY. 


I. According to Witscai the testis of a newly metamorphosed 
Rana fusca is composed of a great number of short tubules, the 
testis-ampullae, whieh end blindly, and are implanted around and 
perpendicular to a longitudinal stem, the central strand. With this 
central strand the mesonephros is connected by the sexual strands. 
The ampullae, which possess a lumen, disappearing later on, form 
no anastomoses and are not branched. Later on the rete testis 
originates from the central strand, the vasa efferentia from the 
sexual strands. 

II. During the further development of the testis, the testis-ampullae 
increase in length as well as in diameter and they simultaneously 
divide towards the periphery into a great number of branches, which 
nearly all grow out till they reach the periphery. Only a few short 
tubules, not reaching the testis-surface, were noted. 

Ill. The testis-tubules of an adult frog, are composed in the same 
way: towards the periphery they split up more and more. All tubules 
terminate in blind ends, and they never form anastomoses. The 
tubules, which are straight near the periphery, are offen somewhat 
bent and twisted near to the rete. 

IV. In two testes of immature frogs it was observed that a small 
caudal part of the testis is not connected with the rete, but that 
the tubules, composing if, opened directly into an efferent duct. 

V. The courses of the vasa efferentia of six immature frogs in 
the beginning of the second year show several peculiarities : 

1. A real network, as in adult frogs, was not noted. 

2. In the fat-body short tubules often occur, neither connected 
with the testis nor with the kidney. 


112 


3. In some cases the cranial part of the rete testis is connected 
with the kidney by an efferent duct, which first passes through the 
fatbody. In one case a short side-duct, coming from the fatbody, 
opened into such a duet. 

4. It was oftén observed that vasa efferentia, which run close - 
together, fuse. This fusion can take place near the testis as well as 
near the kidney. 

5. In a few cases an efferent duct was found, which, originating 
from the mesonephros, did not reach the testis. 

6. The vasa efferentia between rete testis and mesonephros number 
from four to nine, this agreeing with the number, observed in adult 
frogs. In the left and the right testis of the same animal the number 
can vary. 


Utrecht, April 1922. Zoological Laboratory, Vetermary College. 


LITERATURE CITED. 


Bremer, J. L. 1911. The morphology of the tubules of the human testis 
and epididymis. Amer. Journ. of Anat., Vol. 11. 

De Burtet, H. M. und De Ruiter, H. J. 1920. Zur Entwicklung und Morpho- 
logie des Saugerhodens. I. Der Hoden von Mus musculus. Anat. Hefte, Bd. 59. 

De Burvtet, H. M. 1921. Zur Entwicklung und Morphologie des Sduger- 
hodens. II. Marsupialier. Zeitschr. f. Anat. u. Entw., Bd. 61. 

Curtis, G. M. 1913. Reconstruction of a seminiferous tubule of the albino 
mouse. Proc. Amer. Ass. of Anat. Anatomical Record, Vol. 7. 

—— 1918. The morphology of the mammalian seminiferous tubule. Am. 
Journal. of Anat., Vol. 24. 

Gaupp, E. 1904. Anatomie des Frosches. III Abt. Braunschweig. 

Houser, G. C. and Curtis, G. M. 1913. The morphology of the seminiferous 
tubules of Mammalia. Anat. Record, Vol. 7. 

Wirscui, E. 1914. Experimentelle Untersuchungen iiber die Entwicklungs- 
geschichte der Keimdriisen von Rana temporaria. Arch. f. Mikr. Anat., Bd. 85, 
Il. Abt. 

—— 1921. Der Hermaphroditismus der Frésche und seine Bedeutung fiir 
das Geschlechtsproblem und die Lehre von der inneren Sekretion der Keim- 
driisen. Arch. f. Entw. Mech., Bd. 49. 


ABBREVIATIONS. 
c.p. =corpus adiposum, fat body. 
c.str. = central strand. 
I = interstitium. 
n. = kidney. 
feb = peritoneum. 
R. = rete testis. 
s. sty. = sexual strand. 
in = testis. 
ta. = testis-ampulla. 
ts. = tubuli seminiferi, testis tubules. 


v.e. —=vas efferens. 


Mathematics. — “A New Method for the Solution of the Problem 
of the Characteristics in the [numerative Geometry.” By 
G. Scnaake. (Communicated by Prof. Henprik pr Vriks.) 


(Communicated at the meeting of April 29, 1922). 


§ 1. In this paper a general method will be set forth for the 
determination of the expressions through which the problem of the 
characteristics in the enumerative geometry is solved. These are the 
expressions indicating how many individuals two algebraical systems 
resp. of oo? en wo” figures, depending on 2 parameters, have in 
common. 

The method in question will be best explained by application to 
a special example. We shall therefore by the aid of it solve the 
problem of the characteristics for the straight line in a space of an 
arbitrary number of dimensions. *) 


§ 2. We shall first confine ourselves to the straight lines of a 
plane V. In V we assume a point C' and a straight line ¢ by the 
aid of which we represent the plane homographically on itself. 
With a view to this we associate to a point P of V the point 2” 
of the straight line CP that together with C, the point of inter- 
section C’ of CP and ec, and P’ forms an anharmonic ratio that 
is equal to a constant number A. Through this transformation a 
straight line / of V is transformed into a straight line /’ cutting 
lone. 

Especially we consider the transformation for which 40. In 
this case for an arbitrary point P the distance C’P’ =O, so that 
the point P’ corresponding to a point P generally lies in the inter- 
section of CP with c. If, however, P lies in (, together with the 
straight line CP also the distance C’P’ becomes indefinite, so that 
to the point C all the points of V are associated. 

For an arbitrary straight line / the corresponding line /’ coincides 


with c. If, however, / passes through /, there are ow! 


associated 

1) Cf. for other applications Cap. Vi of my academical dissertation which will 
shortly appear, entitled: Afbeeldingen van figuren op de punten eener lineaire 
ruimte, Groningen, P. NoorpHorr, 1922. 


114 


straight lines, which form a plane pencil that has the intersection 
of / and ¢ for vertex. 

If 2 changes continuously, out of a system S of o* straight lines 
through the homographie representation described above, oo’ new 
systems are derived forming a coherent set, which contains S (for 
2=1) and of which we shall especially consider S’, the system 
arising from S through the transformation belonging to A=0. The 
number of straight lines which a system of this set has in common 
with asystem of o! straight lines not belonging to the set, is apparently 
independent of 2. In order therefore to know how many straight 
lines S has in common with another system S* of o* straigh lines, 
we may equally well investigate the same for S’. 

Now any straight line of S is transformed into the line ec, which 
may always be chosen outside S'. If, however, S contains & straight 
lines 7 passing through an arbitrary point, so that & is the class 
of the curve enveloped by the lines /, the & straight lines of S 
through C are transformed into as many plane pencils of straight 
lines /'. S* contains £° lines of each of these plane pencils, if the 
straight lines of S' envelop a curve of the class £’. From this we 
conclude that S' and S', hence also S and S$’, have &k straight 
lines in common. 


§ 3. In order to apply the same method to the straight lines of 
space, we assume a point C and a plane y, and we make use of 
the homographie representation arising if to each point P we associate 
the point P’ that forms with ©, the point of intersection C’ of CP 
with y, and P an anharmonie ratio = 4; in this representation there 
corresponds to any straight line / another straight line /’ cutting 7 
on y. If again we take the case 20, to any straight line / a 
straight line /' of y is associated, the intersection of the plane (C, 1) 
with y, unless 7 passes through C’ in which case there are oo? 
associated lines /’, which form a sheaf of rays that has the point 
of intersection of / and y for vertex. 

In this way a ruled surface 2 is represented in a system &’ of 
»' rays /' of y. These envelop a curve of the class @, if @ is the 
order of Rk. For through a point P of y there pass those straight 
lines /' that are the images of the straight lines / of R cutting CP. 
If now we consider a complex A of the order x, this has in y 
»' rays enveloping a curve of the class x, so that A has x@ rays 
in common with R’. 

A line complex of the order x has therefore xg lines in common 
with a ruled surface of the order go. 


115 


Through our transformation a congruence G' passes into a system 
7 that consists first of all the rays of y, each counted (-fold, if 
8 represents the class of G. For each line /' of y is associated to 
the 8 lines / of G lying in the plane Cl’. Further, if @ is the order 
of G, there are « rays of G which pass through C' and are trans- 
formed into as many sheaves of rays of G’. Another congruence 
with the order @ and the class 3’ has ea’ + Bp’ rays in common 
with G’. From this follows the well known theorem of Hatpawn: 

Two line congruences (a,p) and (e', B') have aa’ + 23’ lines in 
common. 


§ 4. Before we give the general solution of our problem in an 
R,, we consider the special case that we have to do with the a‘ 
straight lines of an &,. By the aid of a point C' and a space I in 
R,, we arrive at the o' homographic representations that are each 
characterised by a value of the anharmonic ratio 4=(CC’PP’) if 
C’ is the point of intersection of CP en I. Again we consider 
especially the representation belonging to 4—= 0. 

If we take a system S, of o' rays, this is transformed by the 
latter representation into a ruled surface S,’ of the order @ lying 
in I, if @ represents the number of straight lines of S, cutting a 
plane. If we consider further a system S, of o® straight lines 
of which an arbitrary plane pencil contains x, the rays that S, has 
in common with J’ form a complex of the order x, so that S,; con- 
tains ox rays of S,’. 

A system S, of the order 9 has 9% rays in common with a system 
S, of the order x. 

A system S, of o? rays is represented on S,’, a congruence 
(a, 8) of I’, if @ is the number of rays of S, cutting an arbitrary 
straight line (through C), and p the number of straight lines of 
S, lying in an arbitrary space (through C). A. system S, has a 
congruence (~,w) in common with I) if g and w represent the 
numbers of straight lines of S, resp. belonging to a (three-dimen- 
sional) sheaf of rays or lying in a plane. S, has «gy —+ Bw rays in 
common with 3S,’. 

A system S, (a, 8) has apm + Bw rays in common with a system 
S, (Pp, w). 

A system §S, is transformed through our representation into a 
system 3,’ consisting first of a complex of the order » lying in T, 
if » ig the number of rays of JS, lying in a (three-dimensional) special 
linear complex. Further, if S, contains w rays through a given point, 
to each of the mw straight lines / through C there are associated the 

8 

Proceedings Royal Acad. Amsterdam. Vol. XXV. 


116 


3 


»* rays / passing through the point of intersection of 7 and IT, so 
that SS,’ contains also «w four-dimensional sheaves of rays. If besides 
D> 


3? 


we have another system |S,’ with the characteristic numbers 


u, and »,, this has in /” a ruled surface of the order », and it 

contains uw, straight lines of each of the four-dimensional sheaves in 

Si’. Sj) and S,’ have accordingly wu, + yr, rays in common. 
Two systems S, (u,v) and S,* (,,%,) have wu, + vr, rays in 


COMMON. 


§ 5. Bij means of complete induction the following results may 
be easily proved, through which the problem of the characteristics 
is solved for the straight line in Ff). 

The characteristie numbers of a system JS, of oo” rays in Ing 
indicate how many straight lines of JS, there are inan Feed lying 
in R, which eut an R,4,—), 2 in the aforesaid R,_,41 forall values 
of p satisfying the inequalities: « > 0, n+ 4—p—2<cn—u-+l 


n+u—p—2>—1 orp >p—n-+. 
From this follows that the p-fold number of characteristics for 


the straight line in &,, if p<, is equal to ae Ss ily 


or ul 


according to whether p is odd or even, and = p2n vere to 
2(n—1)—p-+-1 a. 2(n— 1) — 

2 2 
or even. The p-fold number of characteristics is, therefore, equal to 
the 2(n—1)—p-fold number. 


ing according to whether p is odd 


The expression indicating how many lines an S, and an Son—1)— ap 
have in common, is a polynome of which all the terms are found 
by multiplying each time those characteristic numbers of S, and 
Son—1)-» that belong to conditions which together define a straight 
line in R&,. 


§ 6. It is clear that the indicated method may also be applied to 
the case when we have to do with figures composed of a definite 
number of points, straight lines, planes ete. If the parts of these 
figures are independent of each other, it will often be desirable 
to transform them by different homographic representations. 

The system eg. of the oo” groups of n points (P, P,,..., Pn) of 
a straight line / may in the following way be represented homo- 


graphically on itself. We assume on / 2n arbitrary points (,..., Ch, 
Pr stes. /, and associate to a point P; of a group of m points 


(n-group) the point P'; defined by: (C; 7; P; P's) = 4. 


ANG 


If we take all 2;=0, there belongs to an arbitrary n-group the 
n-group (/°,,...,/°,); if, however, a point P; coincides with C;, 
the associated point 7';, becomes indefinite, so that to an n-group of 


i lire Ar! Pi, coincide resp. with Ci, Ci, Ro Ci, 


there are associated a* groups that have the n—A/ points Pipa La Vr; 
C t 


which the £ points P; 


in common. 
er : n 
Let us now consider a system S, of o* n-groups with the i 


characteristic numbers ¢;, ;,...:,, indicating how many groups of 


th 


the system there are for which the points Re Peed WP 


, 
k 
fined. Through our representation S; is transformed into a system S'; 


are de- 


n 
is 
formed e.g. by the n-groups that have their points Piya S Bi eee 
ti, and of which the remaining points P are 


consisting ot ( ) separate systems of o* groups. Such a system is 


resp. in re qane 
indefinite. Each group of this system is associated to the «%, i, . . hy 


Ci a] Y 
i,m Ci, MO eee Ci, and 


is therefore an a;,;,..-;,-fold group of S'. If we take another 


groups ot S, that have their points P,,..., P 


system S,-; of o"—* proups, with the characteristic numbers 
Pisig-+-i,_,, We find from the number of common groups of 


S', and S,—¢: 

A system Sp (ei, ---i,) 0f w* n-groups of points has with a system 
Pare e(Bi> =: i: 4) of «—k n-groups 24, vss ip Biggs -++i, groups m 
common. 

Finally we remark that the expounded method may also be 


applied to curves, surfaces etc. 


Physics. —- “On the diffraction of Réntgen-rays in liquids.” By 
Prof. W. H. Keresom and Prof. J. De Smevr. (Communication 
N°. 10 from the Laboratory of Physics and Physical Chemistry 
of the Veterinary College). (Communicated by Prof. H. 
KAMERLINGH ONNKS.) 


(Communicated at the meeting of March 25, 1922). 


§ 1. Introduction. The investigation by means of Rontgen-rays 
of the structure of substances that are in liquid or solid state at 
temperatures lower than the ordinary one, seems us to be of extra- 
ordinary importanee. These substances namely belong to those that 
possess the most simple chemical structure (in the gaseous state 
several of them are mon- or diatomic). In most eases their molecules 
consist of light atoms small number of electrons). Therefore the ex- 
perimental results obtained with these substances will lead more easily 
than other ones to conclusions of importance for the structure not 
only of the erystalline state but also of the molecule and the atom. 

We thus gladly followed the invitation of Prof. Kamer.incH ONNus to 
make such an investigation on the diatomic elements oxygen, nitrogen, 
if possible on hydrogen ete. and the monatomic elements as f.i. argon. 
In the discussion of the scheme for this investigation, for which we 
made at Leiden some preparatory experiments, the first question 
was the following: Will liquefied gases also give a diffraction figure 
when they are crossed by a beam of Réntgen rays as it was the case 
with the liquids that were investigated by Drpise and ScHerrer*) ? 
As some Réntgen-technical difficulties had to be overcome we 
agreed to continue the preparatory experiments at Utrecht, as far as 
we should be able to obtain there the liquid gases and work there 
with them. Some of the results of these experiments will be given 
in this paper. In these investigations we did not only use liquid 
oxygen and argon’) but also some substances that are liquid at 
ordinary temperatures. : 


§ 2. The apparatus. Fig. 1 shows the vacuum glass g and fixed 

1) P. Depise and P. Scuerrer, Nachrichten Gottingen 1916. 

*) The argon was put at our disposal by N.V. Philips’ Gloeilampenfabrieken, 
for which we wish to express here our thanks 


119 


to it the camera ¢, into which the liquid gas is poured and in whieh 
it will be radiated by the Rontgen beam which is bounded by the 
diaphragm d of tin (length 34 mim., diameter of the opening 2 mm.) 
shut by a leaf of aluminium. The lower 
part of the inner tube is narrow. First 
it consisted of a small tube of aluminium 
thick 0,015 mm. and with a diameter of 
3 mm. which was soldered to a copper 
tube by means of wolframine. Later on this 
aluminium tube was replaced by a glass 
tube thick 0,002° to 0,01 mm. !) and 
with diameter 2 mm., blown to a wider 
glass tube. Except between 6, and 4, the 
glass was silvered. 

The camera (radius 27,5 mm.) is fixed 
to the outer glass by means of a ground 
plug. In the camera along the cylinder 
wall the film / is stretched (Kastman 
duplitized X-ray film) in the same way 
as was done by Design and Scurrrir. For 
taking in and out the film, which was 


wrapped up in black paper, the camera 
Fig. 1. was detached from the plate p to which 
its ground border had been cemented. The vacuum was obtained with 
a LANGMUIR condensation pump with the rotating mereury pump of 
Garpu as a forepump. This vacuum sufficed to expose with one single 
filling of 200 eM?* of the liquefied gas during more than 5 hours. 
The Rontgen-rays were excited by a metal SteeBann tube with 
Cu-anticathode. The AK, rays were filtered away by a Ni-plate of 
0,01 mm. The current given by an inductorium with gas interruptor 
was + 10 mA., tension + 25 KV., time of exposition as a rule 
5 hours. 
For a photograph of the RoOntgen interference figure of ice (see 
§ 3) we used a glass tube partly filled with water. The lower part 
of this tube consisted again of wu thin glass tube as described above. 
The tube with water was let down into a vacuum vessel with a 
lower part of thin-walled glass filled with liquid air. During the 
exposition the tube was rotated from time to time. 


') These thin tubes of aluminium and glass are proofs of the ability of the 
amanuenses lst class J. J. VAN DER Suuis and A. R. B. Gwrrirse, the last of 
whom has also made several of the here mentioned photographs. 


120 


The substances that are liquid at ordinary temperatures were 
exposed in a more simple glass apparatus with a thin walled lower 
part, which fitted on the same camera, while again the camera 
was evacuated. 


§ 3. Results. We have exposed liquid oxygen, liquid argon, benzene, 
water, aethylaleohol, aethylaether, formic acid, carbonic disulphide, 
bromium. 

Of these carbonic disulphide and bromium (in glass tube) gave 
no distinet diffraction figure *). 

The other liquids gave first an intense almost circular diffraction 
ring. Fig. 2 shows the diffraction ring of oxygen. 

Argon was exposed twice, once in an aluminium tube and once 
in a glass tube. Of these only *) the first one gave a distinct diffrac- 
tion figure. 

In table I @ represents the half top-angle of the cone formed by 
the diffracted Réntgen rays. 


TABLE I. 
3 Su 
Substance a) a 1.33 YR 
oxygen 7a fe 4.0A 4.0A 
argon 27 4.0 4.1 
benzene 18 6.0° 5.9 
water 29 Shp 3.6 
aethylalcohol 22 4.9 See 
aethylaether 19 Sis 6.2 
formic acid 24 4.5 4.5 


By the agreement between the diffraction rings of oxygen and 
argon we might come to the hypothesis that these rings are due 
to the same impurity f.i. to small ice crystals. This was however 
proved to be not the case. Therefore oxygen namely was first dried 
by KOH and P,O,, then liquefied and destilled in apparatus dried 
beforehand and finally poured through a filter of cotton wool into 


') The probable reason for this is, that the Réntgen rays are absorbed to such 
a high degree by these substances, that the Réntgen-light diffracted by the liquid 
on account of its small intensity cannot be distinguished from that diffracted by 
the glass. 

1) Probably by the reason mentioned in note 1. 


121 


the vacuum glass that was filled with dry air’) and in whieh such 
a filter was placed again at the entrance of the narrow part. This 
oxygen now’ gave the same ring. On the other hand a photograph 
of ice (see § 2) surrounded by liquid air taught us that none of the 
interference lines of ice coincide with the ring of oxygen. 

The diffraction image of water shows still an interesting detail 
(see fig. 3 of the plate). Immediately following on the intense diffrac- 
tion ring the film shows a very considerable almost uniform blackening 
with a rather sharp outline at @—= 46°. 

For some other liquids too we found weak indications of a similar 
blackening. 

For oxygen and argon the best films show beside the ring given 
in table I still a weak second ring, for oxygen at y= 46°, for 
argon at m= 49°. 


§ 4. The intense diffraction ring is due to the cooperation of 
neighbouring molecules. As was shown by Exurenenst*) and at the 
same time by Desi and Screrrwr (l.c.) a diffraction ring like that 
of §3 may be due to the interference of RoOntgen-rays diffracted by 
arbitrarily orientated systems each of two (or more) particles, 
which have a definite mutual distance (f.i. the two atoms in a 
diatomic molecule, where each of the atoms is regarded as one 
single diffracting centre.) Between the angle g and the distance a 
of the two diffracting particles we have then (see Kurenrest l|.c.) 
the following relation 

7,722 
CEPT ei ei nities “0 3 (1) 


4 7 sin — 
9 


a 


4 


where 4 is the wavelength of the RoOntgenrays. 

The values of a calculated in this way (with 4 = 1,54 A) are 
given in table I. 

In the first place the fact, that also argon has a similar diffrac- 
tion ring, involves that, at least for argon, this diffraction ring is 
not due to the cooperation of atoms in the molecule. *) 

That this is neither the case for oxygen is to be expected by the 


1) By a small window v in the vacuumglass we could state that the liquid was 
perfectly clear. 

3) P. Enrenrest. These proceedings Vol. XVII, p. 1184. See also P. Desig 
Ann. d. Phys. (4) 46, p. 809, 1915 

3) Unless argon should be more-atomic in the liquid state, which is not made 
probable by the following. 


122 


improbable if not impossible great distance, which the centres of the 
atoms should have then (see table I). 

The distance of the interfering particles calculated with (1) however 
agrees with the distance of the centres of neighbouring molecules, 
when we think us these arranged as the centres of spheres packed 
possibly close together. This distance is found in the last column 
of tabel I (J/= molecular weight, d= density). Small deviations, 
as far as they do not fall within the limits of experimental accuracy, 
might be ascribed to deviations from the spherical form or to the 
circumstance that will be discussed in § 6. 

From this we think it justified to draw the conclusion, that the 
intense diffraction ring found above is caused by the interference of 
Rontgen light diffracted by neigbouring molecules *) *). 

For benzene too the above mentioned agreement between a and 
the distance of neighbouring molecules arranged in closest packing 
has been stated. From this we think it evident that the above con- 
siderations also hold for this substance in contradiction with the 
opinion of Desue and Scnerrer (L.e¢.) that this diffraction ring should 
be due to the atoms in the molecule. 


§ 5. When our view that the observed diffraction ring is due to the 
interference of Rontgen light diffracted by neighbouring molecules 
is right, the dimensions of these diffracting particles may no longer 
be neglected compared with their mutual distance and we may ask : 


1) This does not involve that we have to do with the cooperation of only two 
molecules at a time. On the contrary, as far as it is not due to the particular 
form of the relation between the quantity of Réntgen light and the blackening of 
the film caused by it, the relative sharpness of the diffraction ring might point 
at a cooperation of more molecules at a time. 

These molecules might then be arranged in the liquid in groups more or less 
regularly under the influence of the forces which below the melting point condition 
the regular structure in the crystalline state. 

In this way fi. both rings of argon might be explained by assuming that in 
the liquid a great number of groups is present in which the atoms are arranged 
in a centered cubical lattice. The mentioned rings correspond then to the planes 


(110) and (211), the edge of the lattice would be 4,65 A. ‘Kor the distance of 


two neighbouring atom centres follows then again 4,0 A as in table I. 

Because of the perfect analogy in the behaviour of oxygen and argon we should 
have to replace for oxygen these atom centres by molecule centres. [Later experi- 
ments have shown that the ratio of the values of sin14/, 9 for the two rings does 
not quite agree with the ratio 1:3, as should be the case if the supposition 
made above were valid. Added in the translation]. 

2) The possibility of this has already been acknowledged by DrsisE and 
SCHERRER (l.c.). 


123 


in how far may we regard the distance calculated with (1) as the 
distance of the centres of the molecules? 

As in reality the electrons are the diffracting particles, this question 
may only be answered when the true position of the electrous in 
the molecule is known for every instant. 

In order however to form us still an opinion in this problem we 
shall consider the case of molecules each consisting of a nucleus 
(which is supposed not to contribute to the diffraction) and one 
electron that is freely moving in a sphere with radius r (so that 
it passes in all volume elements equally long times). A system of 
arbilrarily orientated pairs of such molecules all with the same 
distance a between the molecule centres gives then in a direction 
which makes an angle g with the direction of the incident light 
an intensity proportional with 


Ssinar—arcosar'? sinaa 
1 : (2) 
ab 7? aa 
when 
40 . @ 
a = — sin— Saree, SECs. Be wails AO) 
7) 2 


This expression may be easily deduced by an extension of the 
calculation given by Enrenrest for the case of two simple diffraction 
centres. 

When r is not small compared with a, the first maximum does 
no longer correspond .with the relation (1). In this case an other 
factor must be substituted for 7,72 in this formula. When f.i. we 
take a=4A, 7a A. this factor is 7,42. 

Evidently the influence of the dimensions of the molecule is small. 
The more will this be the case as the (mean) density of the electrons 
in the molecule is greater in the ceitral parts than near the periphery, 

When the molecules come so near to each other, that they are 
in conctact the influence is greater. For the simple molecule models, 
described above, the factor in (1) would then become 10 °/, smaller. 


§ 6. Water. The blackening which is found in the diffraction 
image for water round the above mentioned diffraction ring seems 
to point at a rather great number of pairs of molecules with a 
mutual distance smaller than that wich we shall call here the 
normal one’). On_ this supposition the limit of this blackening 


1) With the above is in good agreement, that in table I the mean distance 


(3,6 A) for water is smaller than the normal one (38,75 ‘A). 


124 


f — 46°) corresponds to the smallest distance between the centres 
of two neighbouring molecules. Formula (1) gives for this 2,4 A. 

The further examination of the blackening in the diffraction image 
of the liquids thus gives a direct method of research for the way 
in which the molecules are distributed in the liquid as to their 
mutual distances. Some conclusions may be drawn then also on the 
field of force of the molecules. 

The fact, that in water a_ relatively great number of pairs of 
molecules occurs with a distance smaller than the normal one will 
be related with the peculiarities in the thermodynamic properties 
by which water is regarded as an associating substance. However, 
we do not find an extraordinarily great number of double or multiple 
molecules wlich should have been formed by juxtaposition of simple 
molecules so as to ly as close as possible to each other. 


§ 7. Oxygen and argon. By analogous considerations as in § 6 
we probably must ascribe the second weak ring for oxygen and 
argon to pairs of molecules which touch each other ’). 

According to xi ) this would give for the distance of the centres 


for oxygen 2.4 A, for argon 2.3 A. 

Because of the last remark of § 5 these values might howerer 
still undergo a small variation. 

Comparing these results with those obtained for water we find: 
firstly, that in oxygen and argon there is a considerably smaller 
number of pairs of molecules with a distance below the normal one, 
secondly that for oxygen and argon in the greater part of these 
molecule-pairs the molecules are lying together as close as possible. 

We might ascribe this different behaviour to a difference in the 
fields of force: the water should have then a more intense field, 
which extends over a greater distance, while oxygen and argon 
should have a field of foree which makes itself more felt in the 
immediate neighbourhood of the molecule. In this way the dipolar 
character of the water molecule becomes manifest on one hand, the 
quadrupolar (resp. perhaps octopolar) character of the oxygen and 
the argon molecule (atom) on the other hand. 


! See also p. 122 note 1. 


W. H. KEESOM and J. DE SMEDT: ,,On the diffraction of Réntgen- 
rays in liquids.”’ 


Bigie2: 
Oxygen, with Kz-rays of copper. 


Fig. 3. 
Water, with Az-rays of copper. 


Proceedings Royal Acad. Amsterdam, Vol. XXV, 1922. 


2 


Physics. — “The crystal structure of germanium’. By Dr. N. H. 
KoLkmewer. (Communication N°. 11 from the Laboratory of 
Physics and Physical Chemistry of the Veterinary College at 
Utrecht). (Communicated by Prof. H. Kamertinca Onnns). 


(Communicated at the meeting of April 29, 1922). 


§ 1. Introduction. From a medical-biological point of view too, 

a possibly complete knowledge of the quadruvalent elements as f.i. 
C and Si will be of great importance. The only one among the 
elements of the fourth group of the periodic system the crystal 
structure of which has not yet been investigated is germanium’). 
_ For this reason the author undertook the investigation of this 
structure with the same apparatus that lad already been used in 
the investigation of tin?) and in that of NaClO, and NaBrO,’), that 
has been described in preceding papers. Only the diaphragm of lead 
in the camera was replaced by one of tin*) while before it a Ni- 
filter of 0,01 mm. thickness was placed in order to weaken the 
6 radiation from the Cu-anticathode. The germanium (from Dr. Tu. 
ScntcnarDt, Gé6rlitz), in the form of a fine powder, was cemented 
to a thin glass rod, with Canada-balsam. , 


§ 2. The crystal structure. The observations were in good agreement 
with a structure like that of diamond. In the table this is evident 
from the satisfactory agreement between the values of sin’? 46°) 
derived from the observations with the caleulated ones. For the 


° 
latter we chose as value of the lattice parameter a—5,61 A. From 
the density at 20°,4 viz. 5,459°), the atomie weight 72,4187) and 


the number of AvoGapro 6,062 .107* we deduce a= 5,594 IN 


1) As has been remarked by D. Cosrer (These Proceedings 21, 1294, 1919) 
the knowledge of this structure might also be of importance for the question of 
the eventual existence of binding rings of circulating electrons. 

8) A. J. Buu and N. H. Kotkmeirr. These Comm. Nos. | and 2. These Pro- 
ceedings 21, 405, 494, 1918. 

8) N. H. Korkmewer, J. M. Bruivorr and A. Karssen. These Comm. N°. 5, 
These Proceedings 23, 644, 1920. 

4) W. H. Keesom and J. De Smepr. These Comm. Nr. 10. These Proceedings 
25, 118, 1922. By a sufficiently high tension the L-radiation of the Pb might 
namely be excited by the heterogeneous radiation of the Cu, which would cause 
a blackening of the film. For tin this is much less probable. 

5) 6 is the angle between the rays incident on the substance and those diffracted 
by it. 

6) Ct. WINKLER, Journ. f. prakt. Chem. 34, 177, 1887. 

1) J. H Mituter, Journ. Am. Chem. Soc. 43, 1085, 1921. 


126 


Calculated '). 
Observed. SS == ] 
z-lines. I B-lines. 
Intensity|sin2! 26.108 hy hg hg |sin?!/29.103) Intensity | hy hy hg |sin?'/29.103) Intensity 
| 
vs 59 ae 56 | 
vi 124 | | 220) 122 1.5 
s-vs| 153 || 220) 151 1.5 
fff 168 Wess tha 167 11 
S—Vvs 207 3) pli 207 a) 
f 2495 | | 400| 243 0.4 
f 206 || 400] 301 0.4 | 331] 289 0.6 
m--s | 363 3 Sil 358 06 || 422 363 1.0 
S—Vsulin 45490 liter 2a B42 1.0 
f (double) 511 | 3 3 P4508 0.6 4 aie ou 
f 5995 | 440) 603 0.4 || 620] 609 0.6 
gm || 652) Salles mie cso 0.7 ||| 5.3.3 | aaa 0.3 
m 45 |620| 753 06 | 55 if 716 0.5 
f 801 1533] 810 0.3 
ff 848 642| 852 0.9 
f go2. | 444] 904 0.2, 15 2: 3h gga 0.6 
s—m | 948 35 at) i960 05 || 
f 966 | |800| 974 0.1 
m | 994 | 7:3 3| 1019 0.2 
| | 


From the fact that of ©, Si, Ge and Sn we know modifications 
with the same structure as diamond, while this is not the case for 
Ti, Zr and Th, we might conclude that C and Si are somewhat 
more intimately connected with the elements of group [V4 than 
with those of group 1Va. 

To Prof. Dr. W. H. Krrsom I am much indebted for his interest 
and his kind help in this investigation. 


1) In the calculation of the intensities, only the structure factor, the LORENTz- 
factor and the number of planes factor have been used, not the polarisation factor 
and the temperature factor. 


Physiology. — “An Objective Method for determining the Co- 
agulation-time of Blood.” By R. J. Wot.vius. (Communicated 
by Prof. A. A. HigMans vaN DEN Beran.) 


(Communicated at the meeting of December 23, 1921). 


The usual methods for determining the coagulation-time of blood 
aim at detecting the right moment at which the phase of complete 
solidification of the blood has just set in. 

At first | myself adopted the method suggested by Fonio and 
Frank, viz. by observing, with strict precaution, the coagulation of 
the blood on a watchglass and by noting down the moment at 
which the phase of complete solidification had apparently been 
reached. However I was always in doubt whether complete solidifi- 
cation had been accomplished at a certain moment, or whether it 
had not, so that I always hesitated in fixing the right moment. 

In this connection Hayrm’) says: “On sait, en effet, que la solidi- 
fication du sang ne se fait pas brusquement, c’est a dire d’un_ seul 
coup, & un moment précis. Le phenomene, évolue d’une maniere 
progressive, a tel point, que pendant une periode relativement assez 
longue, on reste dans |’hésitation, en se demandant si la prise en gelée 
est effectuée ou n’est encore qu’imminente.” 

What tells most against these methods, is that the degree of 
solidification has to be determined by subjective observation. I, there- 
fore, looked for some phenomenon that goes on pari passu with 
the solidification and admits directly of measurement. | found that 
phenomenon in the turbidity which attends the salting out of fibrin 
and consequently decided to measure it. Preliminary experiments 
had shown that at the very outset of thickening of the blood a 
clouding commences that increases with the further progress of the 
thickening and ultimately remains stable as soon as coagulation 
has reached its completion. Now, it being my purpose to observe 
the time in relation to solidification, | might as well ascertain the 
time taken up by the clouding process. In order to measure this 
growing turbidity | made use of a new apparatus, the extinction 

1) Hayem, Du Sang, quoted from Marcen Briocu, La coagulabilité sanguine 
pag. 22. Thése, Paris 1914. 


128 


meter!) of Dr. W. J. H. Moun, which enables us to measure the 
turbidity from moment to moment. 

The principle of this apparatus may be discussed in a few words: 

A powerful light-souree is firmly set up’ between two surface 
thermobatteries I and II, after Moti. They are both connected to 
a mirror-galvanometer, thus counteracting each other. Between the 
lamp and the thermobattery I is placed a cuvette filled with water; 
between the lamp and the thermo-battery II a cuvette filled with 
the blood-plasm. 

Consequently the light that is directed on to the thermo-batteries 
is weakened on the one side by water, and on the other by blood- 
plasm. Through displacement of one of the thermo-batteries or through 
changing the position of the lamp the unevenly weakened light may 
be made to fall upon the thermo-batteries with equal force. The 
twe thermo-electrie currents thus elicited, will then be equal, the 
calvanometer will receive a current 0, the image reflected by the 
mirror will occupy the O-position. The apparatus has then been 
“adjusted”. The slightest change in the turbidity of the plasm 
disturbs the equilibrium and yields a deflection of the galvanometer ; 
the apparatus acts so quickly that after a contingent sudden change 
in the turbidity the reflected image will come to rest again within 
a few seconds. Moreover a procentic measurement may be taken 
of the changed turbidity with the aid of a so-called compensation- 
switch. 

Now our procedure is as follows: Into a sterile, dry Record- 
syringe of 10 ¢.c. with a sharp, dry needle, 1 ¢.c. of a clear sterile 
solution of 1°/, potassium oxalate in 0.85 °/, common salt is sucked 
up; the needle is inserted into a cubital vein and the blood is 
aspirated to 10 c.c. Due regard should be given to an easy flow 
of the blood into the syringe, so that no air is drawn in along 
with it. The mixture thus obtained, is centrifugalized during 20 
minutes in sterile centrifugation-tubes, which causes the blood- 
corpuscles and the blood-platelets to precipitate and the supernatant, 
more or less turbid plasm can be pipetted off and transmitted to 
sterile tubes. Three e.c. of this oxalate-plasm (measured very care- 
fully with sterile pipettes) are put into pure, and dry cuvettes. The 
cuvettes used by me are made of the same glass and have precisely 
the same dimensions, so that not only the thickness of the fluid- 
layer, but also the level to which the cuvette is filled, is always 
the same in every one of them; in other words the contact-plane 

1) Dr. W. J. H. Morn, Een extinctiemeter. Verslag Koninklijke Akademie van 
Wetenschappen, Wis- en Natuurkundige Afdeeling, 27 Maart 1920. Deel XXVIII. 


129 


between plasma and glass is the same. This cuvette is placed in 
another one of special construction, which acts as a thermostat, is 
filled with water and is heated electrically. 

The measurement proceeds as follows: 

The cuvette is placed in the thermostat so as to make the light 
of the lamp reach the thermo-battery II and pass through the plasm. 
By its side, in the same thermostat, stands a test-tube containing 
14 cc. */,°/, CaCl,. The extinctionmeter is “adjusted”. Then follows 
a 20 minutes’ wait, after which the plasm and the CaCl, will be 
of the temperature of the thermostat and the galvanometer will be 
completely quiescent and in the zero-position. The work-room is 
made semi-dark and from this moment photographical readings are 
taken from the galvangmeter. A registering instrument is used that 
is moved by a perfectly reliable clockwork. 

After some moments the 14 cc. '/,°/, CaCl, are added to the 
plasm, the whole mixture is rapidly stirred for half a minute with 
a sterile glass rod and is then left to itself. The galvanometer then 
traces on the sensitive paper of the registering instrument the 
“turbidity-curve”. 

Fig. 1 is a faithful reproduction (natural size) of such a curve, in 


C 


130 


which three horizontal portions A, B, and Care to be distinguished. 

A indieates the motionless phase of the galvanometer during the 
time when there is only the oxalate-plasm between light-source and 
thermo-battery ; a. indicates the moment when CaCl, is added; the 
first moment the plasm becomes clearer, see 6., which is owing to 
the dilution of the plasm. But directly after this the liquid becomes 
very turbid which is due to the forming calciumoxalate; the curve 
ascends almost vertically, see c., and would gradually have reached 
the #B-level, if not an irregular weakening of the light had been 
brought about by the stirring rod; the jerks in the curve at d. 
illustrate this irregularity, so that they have nothing to do with the 
process of turbidity. The calcium oxalate is not precipitated but 
remains in suspension; for a few minutes the galvanometer remains 
constant, as shown in the 5-portion. 

Up to this moment coagulation is out of the question. Soli- 
dification commences at e. at a certain moment, apparently quite 
independently from the inital turbidity (formation of calcium-oxalate), 
and simultaneously the second phase of turbidity begins. It is this 
portion of the curve that interests us most. Its shape is an objective 
illustration of the coagulation process. 

It appears that this coagulation starts very slowly, then proceeds 
more quickly until a maximum rate is attained, after which a 
retardation sets in again until the terminal value is ultimately 
reached. 

[ will not discuss here the nature of this curve, but only point 
to the method, which enabled me to typify any given portion of 
the curve by a figure. I note the exact time at which certain levels, 
e.g. '/, and */, of the difference of the B-, and C-level are reached ; 
the time-difference is my control-number. 


My researches were performed in the Physical Laboratory of the 
Utrecht State-University, where I had the freedom of the instruments. 


Utrecht, December 1921. 


Physiology. — “A contribution to the physiology of the electrical 
organ of Torpedo” By Prof. F. J. J. Boyranpiix. (Communi- 
cated by Prof. G. van Rusnperk). 


(Communicated at the meeting of April 29, 1922). 


In the winter of 1911 I had the opportunity to investigate the 
function of the electrical organ of Torpedo in the Zoological Station 
of Naples. The aim of part of this research was to study the 
magnitude and character of its discharges under different cireum- 
stances. For this purpose a string-galvanometer (large type of Eprl- 
MANN) was available at Naples and with this apparatus I made many 
records. From these records and from test-records of the apparatus 
it appeared, that the string-galvanometer is not the most suitable 
instrument for the registration of the discharges of the organ of 
Torpedo which reach their maximum within 0,002—0,003 sec. This 
does not astonish us in connection with the investigations of GARTEN *). 
For this reason [| intended to continue this research with an appa- 
ratus more suitable for this purpose (oscillographion, Fvs1’), string- 
electrometer, Cremrr*). However, as circumstances prevented me 
from carrying out this plan, I now communicate the results of my 
research. 

Marry, ScnoOnnein and Gotcu *) have already observed that the reflex- 
discharge of the electric ray has a rhythmical character. In many 
records I found that as a rule many discharges succeed each other, 


Fig. 1. Reflex-discharge in Torpedo after mechanical stimulation. 
Test-record 4 volt. Time '/;9 sec. 


}) Garren. Abh. d. Kel. Siichs. Ges. d. Wiss. 1899. 
®) Fus. Journ. of the College of Science Univers. Tokio 1914, Vol. 37. 
3) CREMER. Sitz. Ber. Physiol. Geselsch. Berlin 1912. Mediz. Klinik 1912, N°. 42. 
4) S. Garren. Handb. d. Vergl. Physiol. 8e Bd. 2e H., p. 177. 
9 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


132 


mostly 5—8 in number with an interval of 56. Fig. 1 represents 
one such discharge, where the shocks came with an interval of 
5,66. Cremer found an average of 5,66 in reflex-discharge. Most 
striking in these rhythmical discharges is the regularity and the 
equal amplitude of the single shocks, as appears clearly from my 
figure. In the periodical discharges after stimulation of the nerve 
of the excised organ, I never obtained such regularity and asa rule 
inequal amplitude. Usually the shocks diminish gradually, sometimes 
they first inerease, then decrease. Fig. 5a and 56 illustrate this more 
clearly. The periodical discharges in reflex-action therefore give the 
impression of being caused by a series of central impulses from my 
nervous system, whereas the periodical discharges after stimulation 
of the organ or the nerve seem to be due to secondary self-stimu- 
lation. This is especially and to a greater extent true in the case 
of the stimulation of the nerve. After direct stimulation of the organ 
usually only two small, secondary discharges oceur, provided that 
the nerve has been ent at the very spot of its entrance into the 
organ. Foust however has registered reflex-discharges (in Astrape 
japonica) in which only two shocks occurred in every group 
followed by a small one. The same result was also obtained after 
stimulation of the nerve stem. For this reason Fusi believes that 
the successive discharges occur by self-stimulation. The solution of 
this question has importance for the question which has been solved 
by Garten’) in Malapterurus, i.e. in how far the discharges of 
both organs occur simultaneously. 

In a detailed research Bernstein and Tscuermak *) have tried to 
find out whether the current which the electrical organ produces 
during activity is caused by a concentration-chain or whether a so- 
called chemical chain here causes the difference in potential. To 
solve this question the temperature-coefficient of the force of the 
current in the organ was investigated within certain limits of tem- 
perature. 

From theoretical considerations it is known, that in a concen- 
tration-chain the E. M. F. is nearly proportional to the absolute 
temperature. Brrnstem already had found a positive temperature- 
coefficient for the current in muscles and nerves and within normal 
limits of temperature the E. M. F. proved to be nearly proportional 
to the absolute temperature. 

In their study on the electrical organ the authors mentioned above 


‘) Garten. Zeitschr. f. Biol. 1910. Bd. 54. S. 399—430. 
*) BeRNSTEIN und TscHERMAK. Pfliigers Archiv. 1906, p. 112. 


1338 


always stimulated the nerves of the organ by means of a single 
induction-shock (make-induetion) and read the deviation of a galvano- 
meter with not too great inertia on a scale. The deviations of such 
galvanometers are nearly proportional to the average EK. M. F. of 
short currents, if the external resistance and the path of the current 
remain constant. The latter condition, however, was surely not 
complied with at different temperatures. 

From the investigations of Gorcr on the capillary electrometer 
it had already become known that the velocity of the movement 
at low temperature (3° C.) is retarded and differs rather strongly 
from that at moderate temperature (15—20° C.). Such change in 
the record of the current must magnify the movements at low tem- 
perature. In that way-the difference with those found at higher 
temperature is bound to become smaller than corresponds to reality 
and the observed temperature-coefficients must be too small as 
GarvEN has already observed. Moreover, it has become evident from the 
experiments of ScuOnBein and Garten, that after indirect stimulation 
of the electrical organ by induction-shocks a repeated discharge 
frequently occurs, which of course does not show up with the slow 
galvanometer. 

My own experience has shown that especially in the cooled organ 
this repeated discharge occurs very frequently. In this way the very 
low temperature-coefficients, found by Burenstrin and TscHERMAK may 
partly be explained. 

At any rate, it seemed advisable to try to secure more data on 
the process and the E.M.F. of the shock. Of freshly caught specimens 
of Torpedo marmorata and T. occalata the electrical organ was 
prepared free with its nerves after removal of the skin. The organ 
was now enclosed between two zine electrodes by means of two 
rubber rings. Two bars for the conduction of the electrical shock 
were attached to the zine electrodes. 

The conductors were passed through a rubber stopper which also 
held the platinum electrodes used for the stimulation. This rubber 
stopper served to close a glass-vessel, in which the organ could be 
enclosed and through which a stream of liquid could be passed. 
The strength of the electrical discharge could thus be studied under 
different circumstances. 


Moreover, a thermometer was inserted into the stopper. If one 
allows the liquid to flow into the vessel through the lower tube 
(Fig. 2) and to leave the apparatus by the upper one, it is possible 
to regulate conditions so as to keep the organ in the fluid and to 


keep the nerves in the air. 
oF 


134 


This arrangement had the advantage that it enabled me to repeat 
the indirect stimulation under very constant conditions. In this way 


one succeeds in keeping the organ in good condition for 2—3 hours, 


Fig. 2. Apparatus for study of electrical Fig. 3. 


discharge in different fluids, gases /o = electr. organ S = string-galv.m. 
and temperature. /=slate-resistance 7 = induction-app. 
v = volt-meter phos = apparatus for 


w= resistance-box  photogr. registrat. 


so that if one stimulates once every 15 minutes the deviations of 
the galvanometer remain constant. 

The discharge was led to an ordinary resistance-box and a slate- 
resistance (of 800,000 £2). From the resistanee-box a eircuit could 
be branched off to the string-galvanometer. By means of a key, 
connected with the recording apparatus, a definite potential difference 
could be thrown into the chief circuit for the purpose of testing the 
movements of the string (Fig. 3). 

A tuning fork of 50 vibrations per second marked the time on 
the photographical plate, while a very sensitive signal of Drpréz 
indicated the moment of stimulation. The nerves were stimulated 
by means of induection-shocks. Sometimes part of it was thrown into 
the string-cireuit so as to have the string itself mark the moment 
of stimulation. 

It is clear that this method does not enable one to study the 
question of the relation of a stimulus to its effect. 

This question has been thoroughly investigated by Fusi with the 
oscillographion. 

In my experiments I could not state anything but the fact thata 
weaker stimulus gave a less noticeable effect than a strong one and 


135 


that make induction-shocks are more effective than break-shocks (Fig. 4). 
__ ne eis deena To get an impression of the 
ial conditions on which the magni- 
tude of the discharge depends, 

I first investigated the question 


whether organs which had been 


SS SES eee 
Sa OEO kept in different liquids for 


| some hours, as a result showed 
. * a change of the discharge-shock. 


Fig. 4. Example of discharge after Of course, the nerves were 
indirect nerve stimulation with make 


‘ : always stimulated with maximal 
and break induction shock. 


stimuli. 
In this way it appeared that an organ (withont skin) kept in: 


Experiment 1. 

2.5%/, NaCl-solution lost its irritability after three hours. The same thing was 
true for sea water. In Fiihner’s solution + urea!) the irritability strongly diminished 
after three hours. 

Experiment 2. 

Organ 1: in (NaCl 2,5 °/, + KCI 0,1 °/)) no shock could be obtained after 40 min. 

Organ 2: in (NaCl 2,5 °/, + CaCl, 0,29/,). After 40 min. the shock had diminished 
slightly. 

Organ 3: in F. sol. after 40 min. shock not changed. 

Experiment 3 (see fig. 5). 


NaCl ax Fihneesehe oplessing. + 0, 


Fig. 5. 


A preparation made from Torpedo marmorata (size 15 c.m.) from 3.50—4.10, 
Organ 1 is put into NaCl 3°/). From 3.50—5.28 four records were made (fig. 3. 
a, b, c,d), the preparation was then put into Fiihner’s solution + QO . After about 
60 min. record e, after another 38 min. record /, after 20 min. record g. 

1) Fiihner Zeitschr. f. allgem. Physiol. (1908) Bd. 85. 485. 
Used solution was: 


Na,CO; 0.2 

CaCl 0.2 ] 

KC] 0.1 > per 1 L. water. 
NaC] 20. 


Urea? (25: 


136 


It appears that after the discharge has decreased in the NaCl solution, it again 
increases in Fiihner’s solution + Oy. 

The other organ (2) has been kept in moist air from 4.10 until 6.47, then it 
is put into Fiihner’s solution + O,. It becomes apparent that this organ also 
shows a considerable increase in magnitude of the discharge after 30 minutes. 

The result of experiment 3 is therefore that O, causes the shock to increase 
and that sol. I. shows the same activity even though the discharge had been 
weakened by an immersion in NaCl-solution. 

Experiment 4 (Fig. 6 and Fig. 7). 


Fig 6. Fig. 7. 


Preparation of small Torpedo (15 c.m.). 


Organ 1 (Fig. 6): At 8.53 in 3°, NaCl. Record A. After two hours record B. 


O, is now bubbled through the NaCl. Alter 30 min. record (. 


Organ 2 (Fig. 7): At 4.50 in 3°/, NaCl. Record A;. After 70 min. record B,. 


NaCl replaced by Fiikhner’s solution. After 80 min. record Cj. 


Result: Og restores the discharge even if the organ remains in NaCl-solution. 


Sol. F. restores the discharge which has been diminished in NaCl. solution. , 


Experiment 5. 

The preparations were made at 10.30 in the morning. 
Organ 1: kept for 4 hours 40 min. in F. sol. poor in oxygen (boiled), 
Record a: deviation is 0,25 volt. After 14 min. exposure to the air. 


Record : deviation is 0-31 volt. After the preparation had been kept for 23 min. 


in well-aerated F. sol. 
Record c: deviation is 1,4 volt. 
Organ 2: kept for 4 hours 30 min. in F. sol. (O, bubbling through). 


137 


Record @: deviation is 3 volt (followed by a series on spontaneous discharges). 

In F. sol. free of O, the deviation diminishes considerably. After the preparation 
has- been kept for a long time in F. sol. rich in O3, a repeated discharge follows 
after one indirect stimulation. 


In two other experiments in duplicate it could be shown that also 
after keeping the organ in F, sol. which had been saturated with 
H, and more so yet in one with CO,, O, causes the deviation to 
increase. 

After this series of experiments another one followed in which 
the same apparatus was used (Fig. 2). The Fiibner’s solution, poor 
in O, or saturated with, it was here kept at certain definite 
temperatures by immersing the whole apparatus in a thermostat. 


Experiment 8. 

Organ 1: Temp. 18°. Deviation about 25 volt. Latent period 5,5c. 

After 30 min. Temp 11°. Deviation 24,2 volt. Latent period 6,8c. 

After 22 min. Temp. 28°. Deviation 0,3 volt. Latent period 4,2c. 

Organ 2: Temp. 18°. Deviation 20,6 volt. Latent period 6,4c. 

After 40 minutes: Temp. 30°. Deviation 0,25 volt. Latent period 

After 26 minutes: Temp. 15°. Deviation > 4 volt. Latent period 

Experiment 9. 

Piece of organ of large Torpedo between zinc electrodes, two nerves being 
intact. Thermometer lies in immediate neighbourhood of organ. Length of nerves 
15 mm. Distance of stimulating electrodes 3 m.m. 


3,4c. 
6,50. 


eee fe | test | cenation | Degharee | Lat er 

20 5.05 a 4 volt 5 > 40 5.2 
13 Sel 6 4 volt 5 + 30 | 7.5 
AD eal c 4 volt 5 32 12 

6 b= Ges d 4 volt 5 10.5 | 20 

5 6.32 e "ly volt 5.9 OL21 s 22.3 
10 6.47 f 4g volt 9 0.31 16 

15 7.16 g '/, volt ie) 0.67 | 8.7 
15 9 h '/, volt 14 0 


As mentioned before we can not attribute any absolute value to 
the volt-values given for the discharges, since the galvanometer- 
records require a correction which can not be calculated very 
easily. After cooling, however, the string will more easily follow 
the potential difference, because if develops more slowly in the cold. 

Whatever may be their absolute value we can see easily from 


138 


figures of exp. 9 that as long the organ is cooled, up to about 7,5° 
z Ds , , 


the discharge diminishes slightly, though not very considerably. 


From 5—15° a rapid decrease follows with a slight recovery. Tlen 
the organ apparently is dying. 

The changes in deviation of the test-potential were obtained by 
changing the side-chain or the resistance, not by changing the sensi- 
tiveness of the string (tension). 

Experiment 10. 

Large organ, kept in F. sol. containing Qs. 


Time, {ag [eee | Sere ea ae 
m.m. in & 
4.23 5 1 11.5 0.33 12.26 . 
4.38 10 l 14 0.49 9.33 
5:53 19 1 1.5 3.3 5.6 
5.14 26 I Lick) 0.67 4.66 


The temperatures given are presumably not those of the inside of the organ 
because the temperature changed too rapidly. Consequently the large organ conld 
not have assumed the temperature of the environment. 

Heating to above 22° gives a considerable decrease as appears 
from : 

Experiment 11. 

At 3.05 ’o clock. Temp. 21°. 1 volt = 2,6 m.m. Deviation 25 mm. 

At 3.30 ’o clock. Temp. 28°. 1 volt = 2,6 mm. Deviation 2,1 m.m. 

The rise in temperature has diminished the deviation to !/)o. 

Experiment 14. 

At 5 ’o clock. Temp. 20°. 1 volt = 5,5 m.m. Deviation 32 m.m. 

At 5.30 ’o clock. Temp. 25°. 1 volt = 5 m.m. Deviation 17 m.m. 

The rise in temperature has caused the deviation to diminish to !/. . 

In Fig. 8 and 9 the string-record of the discharge at different temperatures 
has been pictured together with the test-record. | have reconstructed it to the 
best of my ability from the not absolutely focussed photographs. 

Large organ in F. opl. at 28° C. (since 12.55). 


Test. 


Time. avant Deviation. 
1 11 5 mm. 35.5 m.m. 
1: 271 5 m.m. 34 «m.m. 


Now 8 stimuli are given at intervals of 30 sec. 


1.31 5 m.m. | 4.8 mm. 


As -., 


139 


In that way it is evident that at high temperatures fatigue occurs 
very rapidly. A attempt to study the influence of O, at different 
temperatures could not be carried out systematically. 


fared 


SG 


(0 0~ 
12 


Fig. 9. 


140 


From the experiments if appeared however that at high tempera- 
tures (22°—28°) O, did not cause an inerease in discharge. The 
latter was the case at lower temperatures. Experiments on the 
influence of narcotics had to be given up at an mopportune moment. 

Fig. 10 demonstrates that by chloral-hydrate the discharge disappears 
uearly completely. 

In the apparatus nerve and organ were kept at the same tempe- 
rature. [t seemed important in order to judge about the change 


g baa on 5 aaa: 
Fig. 10a. Fig. 106. 
a. Record of discharge small electrical b. The same after exposure to chloral- 
organ). Test '/, volt. hydrate dissolved in Fiihner’s solution. 


in the valnes for the latent period, to submit the nerves separately 
to changes in temperature. 

Experiment 16. 

Preparation of large Torpedo (28 c.m.) made between 11.45 and 12.45 and 
put into apparatus. 

Piece of organ with two nerves, the nerves led through glass tubes, m which 
stimulating electrodes. Tubes surrounded by glass-mantle, im which water circulates 
at different temperatures. 

After the experiment has been ended a control is made by tying off the nerves, 
which causes a complete breaking of the conduction. 

The magnitude of the deviation remained the same although the 
temperature of the nerve varied from 20'—6°. 

The values of the latent periods actually were lower at lower 
temperatures. The measurements are, however, not sufficiently 
accurate to allow a calculation of the velocity of the conduction. 
That, however, the differences in latent period found in the other 
experiments are due to changes in the electrical Organ, is evident 
from the fact, that in this experiment the difference between 6°—20° 
only amounted to 1.8 6. 

Having thus obtained an impression on the influence of tempera- 
ture O, and different salt-solutions on the strengih of the discharge 
as a responce to indirect stimulation. I have tried to study the 
gaseous exchange of the electrical organ in rest and during activity. 

For this purpose the electrical organ was enclosed in a very thin 


141 


dialysing sae of collodion. The oxygen of the surrounding liquid 
passes through these sacs without difficulty, as could be shown in 
preliminary experiments, but only a very small quantity of organic 
substances passed through so that the method of Winkier for the 
determination of O, dissolved in water, could be used with a slight 
correction. This very useful method of Winker can only be used 
in the absence of organic substances in the liquid or after a cor- 
rection has been made‘). 

This dialysing sae was put into a bottle, which was completely 
filled with Fianrr’s solution of known O, content. After some time 
(1—2 hours) a certain quantity of the contents of the bottle was 
again secured for a WiNKLeR’s determination of its O, percentage. 

In order to stimulate the organ during its stay in the liquid, two 
silver electrodes were tied to the organ. Organ and electrodes were 
then put into the dialysing sac and immersed into the liquid. The 
organ was stimulated directly once every 5 sec. 

The results are given in the following table: 


TABLE I. 
Exp. Nae Stim. ~ ee a Temp. Nuts ieee ai 6. 
N°, Not-stim. — arte Ones 
gms Not stimul. | Stimul. 
6 35 — 2 18 60 
7 36 = 1/4 18 62 
Ta 36 + Vp 18 103 
8 Al a 1 21 220 
8a Al + 1 19 220 
9 57 — 1 21 103 
9a 57 — 1 19 74 
10 18.3 — 1 21 306 
10a 18.3 + - 1 21 440 
12 28 — 1 6 136 
12a 28 + 1 6 160 
13 41 a 1 19 93 
13a 41 a 1 19 100 


') See Henze Abderh. Handb. der Biochem. Arbeitsmeth. Ill, p. 1067. 


142 


In the first place it beeame evident that though the results varied 


considerably — this is easily explained by the changing condition 
of weight ete. of the organ and the varying conditions for the 
diffusion of oxygen — the figures in the first place give a very 


definite idea about the gaseous exchange in the electrical organ. 
The electrical organ appears to consume 6—18 m.m*. O, per gram- 
hour, a quantity which is of the order of the O, consumption of 
the peripheral nervous system (THunBERG)*) which consumes about 
‘/,, Of the quantity that is used by the central nervous system. 

In 1883 Wevt tried to demonstrate some chemical changes in the 
electrical organ after it had shown vigorous activity. He found a 
change in reaction (hydrogen-ion concentration) i.e. an increase in 
acidity after activity. Moreover, he tried to estimate the production 
of CO, by the organ. Wnhyr found that 17,5 gms. produced 4 mgms. 
CO, in two hours. After stimulation he found a decrease instead of 
an increase. The alcohol-extracts of a stimulated organ and one 
which had not been stimulated, did not show any differences. The 
watery extract of the stimulated organ was larger. 1 myself have 
tried in vain to demonstrate the change in reaction after stimulation. 
I have tried to demonstrate two chemical substances in the electrical 
organ i.e. xanthin-bases and glycogen. This seemed to me to be of 
importance, because we know that the electrical organ must be 
derived from muscles in which both substances occur abundantly. 

The xanthin-bases were determined according to the method of 
Burian : 


100 gr. of the organ are boiled for 12 hours in 1 L. of 0,5°/) HySO,y. After 
filtration the sulfuric acid is precipitated with Ba(OH), and the liquid which is 
now alcaline is filtered. The filtrate is saturated with CO,. The BaCO is removed 
by filtering and the filtrate, after acidification with acetic acid, is evaporated down 
to 100 c.c. These 100 c.c. are boiled for some time with a smaller quantity of 
concentrated NaOH 4+ Na,CO. and filtered. The filtrate is acidified with HCl A 
precipitate of xanthin bases now comes out on addition of an excess of NHs -+ AgNO. 
In this precipitate nitrogen can be determined according to KJEHLDAHL. 


The following table gives the results of this investigation: (See 
Table 2, following page). 

We may therefore conclude that the electrical organ contains no 
xanthin-bases or a neglegible quantity. 

Determinations of glycogen were made in two very large animals 
and in two young ones. 


') Taunsera. Zbl. Physiol. 28 (1904). See also BuyrEnpIJK. Kon. Ak. y. Wetensch. 
1910 (615—621). 


143 


TABLE 2. 
Result. 
Exp=rts 107,5 gm. electric organ. Very slight precip. 
Exp. la. 55 gm. muscle Heavy precip. 
Exp. 2. 106 gm. electric organ. No precip. 
Exp. 3a. 120 gm. electric organ. Very slight precip. 
Exp. 4. 122 gm. electric organ. No precip. 
Exp. 4a. 52 gm. muscle Heavy precip. 
The determination was made according to PELicer: 
TABLE 3. 
Exp. Size of animal in c.m. | Quantity of organ. 9/9 Glycogen. 
: 60) taken out of the 313 0.051 
2 45 | apa 128.8 0.031 
3 15 freshly caught animal. 20 0.787 
4 5 6specim.; just born. 13.5 1.02 


If we compare these results with those of BaGuioni '), we see that 
the glycogen values in exp. 1 and 2 are lower than those given by 
Baaiionr (0,09 °/,), but of the same order. The figures in very young 
animals (exp. 3 and 4) are very much higher. 

If the electrical organ functions by splitting up ion-proteids, 
we may expect salts to become free. This might be the 
explanation of the increase of the watery extract found by Wryt. 
The electrical organ reacts to mechanical stimulation, e.g. mincing 
or pressure, by strong activity. Therefore I have tried to divide 
electrical organs finely by gradually cooling and finally freezing 
them. In that way no discharges occurred. In centrifuging the frozen 
organ after it had been ground up, I could obtain a very complete 
separation of the organ-fluid. This fluid as obtained from stimulated 
and fresh organs, was used for the present research. 

In the liquid thus obtained I made a determination of the ash- 
compounds, which led to the following results: 


1) Baauront. Hofmeister’s Beitrage 1906. Bd. VIII, p. 456—471. 


144 


TABLE 4. 
Ash (mgs per c.c. organ-fluid) determined after the wet method (SO, ash). 
Exp. Not stimul. Stimul. Difference. 
] 31.8 31 — 0.8 
2 30.4 31.2 + 0.8 
3 38.6 35.5 — 3.1 
4 26 28 4k) 


We see at once that there is no difference in ash-content in the 
fluid of a stimulated organ. and of one which bad not been stimulated. 
Moreover | made treezing-point determinations in both liquids. - 


TABLE 5. 
A in ° in organ-fluid. 
Exp. Not stimul. Stimul. Difference. 
| Divli2, 2216 + 0.095 
2.12 2.21 + 0.09 
2 2.145 2.30 + 0.155 
2135 2.295 + 0 160 
3 2.16 223 + 0.07 
2.15 2.24 + 0.10 
4 2.095 2.18 + 0.085 
Ground Ground when 
when frozen. warm (20°). 
5 2.08 2.20 0.17 


From these experiments it appears that during activity substances 
pass into the organ-fluid which must be considered to be organic 
substance, because the ash-content is not increased, whereas the 
freezing point shows a very definite lowering. 

However incomplete these investigations may be, | have felt the 
desirability of communicating them very briefly, the more because 
I shall most probably not be in a position to take up the whole 
problem once more and because the data published in the present 
paper, to my opinion, may be a stimulus to a continued research 
of the physical and chemical processes which take place during the 
discharge of the electrical organ. 


Physiology. — “On the Significance of Cateium- and Potassinun- 
ons for the artificial Oedema and for the lumen of the 
bloodvessels’. By Ruponr J. Hampurcer. (Communicated by 
Prof. H. J. HAMBURGER). 


(Communicated at the meeting of March 25, 1922). 


Of late years a series of researches have been carried out in the 
Groningen Physiological Laboratory, which demonstrated, among 
other things, that the solution used by Smpney Rineer in his remark- 
able experiments on the frog’s heart, is not suitable for other 
organs of the frog. As known, this solution is composed as 
follows: NaCl 0,7°/,, NaHCO, 0,02 °/,, CaCl,6 aq. 0,04°/,, and 
KCl 0,01 °/,. Hampurcer and Brinkman’) found that when, after 
the addition of a little glucose, this solution is allowed to perfuse 
the kidney, the glomerular epithelium does not retain any glucose. 
Systematical investigation, however, enabled them to modify the 
circulating fluid in such a way that the glomerular epithelium 
obtained the property to retain the physiological amount of glucose 
(0,060—07°/,) This circulating fluid was of the following composition : 
NaCl0,5 °/,, NaHCO, 0,2 —0,285 °/,, CaCl,6 aq 0,04 °/,, KCI 0,01 °/,. 
Also for other organs of the frog the proper physiological fluid was 
found after systematical investigation (for the movements of the 
stomach on excitation of the N. vagus’*), for the movements of the 
rectum *), for formation and solution of biliary concrements) *). All these 
researches have shown that the efficiency of the circulating fluid 
depends on the amount of free calcium-ions *). Also in warm-blooded 
animals the concentration of Ca-ions appeared to play a prominent 
part: here we allude to the investigations on haemolysis *) and on 


1) H. J. HamBuRGER and R. BrinKMAN, These Proceedings Vol. XIX, p. 989 
and Vol. XX, p, 668. See also Biochem. Zeitschr. 88, 97, 1918. 

*) BRINKMAN and van Dam, These Proce. 18 Dec. 1920. 

8) Demonstration by van Crevetp at the Conference of Physiologists at Amst. 
22 Dec. 1921, 

4) Bott and Heeres, Ned. Tijdschr. v. Geneesk. 65, 2d half N°. 10, 1921. Also 
Pfliiger’s Archiv f. d. ges. Physiol. (not out yet). 

5) Cf. also H. J. Hampurcer, Permeability in Physiology and Pathology, Lancet 2, 
1055, 1921. 

6) Brinkman, Biochem. Zeitschr. 95, 101, 1919. 


146 


the origin of spasmophilic phenomena consequent on decrease of 
ihe concentration Ca-ions of the blood *). This concentration of depends 
upon Ca-ions the NaHCO, and on the H-ion concentration. 

As for the influence of the concentration of the Ca-ions upon the 
permeability of the glomerular epithelium, it is so great that, even 
when a potassium-free liquid is sent through the kidney, retention 
of the physiological quantity of glucose was still observable ’). 

This being the fact, it seemed interesting to us to investigate with 
what liquid the vascular system of the frog had to be perfused 
in order to prevent the production of edema im the hindlimb. 

We were all the more induced to inquire into this matter, since 
some years back GunzpurG *) occupied himself with this question in - 
the Utreeht Physiological Laboratory. He found that, when perfusing 
the vascular system of the frog with a fluid such as Rineer had 
used for the heart, and which differed from ours in NaHCO, 0.02 °/, 
being used instead of 0,2 °/,—0,285 °/,, KCl 0,01 °/, was indispens- 
able to prevent oedema. So, in GunzpurG’s experiments oedema 
arose when the fluid was potassium-free or when too large an 
amount of K was present. Instead of K he could use also Uranium, 
Thorium or Rubidium in definite quantities. It is evident, therefore, 
that, according to Gunzpurc, K is indispensable in this case, and 
this indispensability is, aceording to him, due to the specifically 
radio-active effect of this element. 

But Gunzpvre also detected that in Rineer’s mixture K could be 
left out, when the mixture was saturated with oxygen, in which 
case cedema was also prevented. We shall revert to this point. 

It has been stated that in the circulating fluid Hampurcrr and 
Brinkman could do entirely without K. In that case, however, the 
Ca-ion concentration should have a definite value. The question 
now arose: can wdema be prevented in the frog's limb with a 
potassium-free circulating fluid, the Ca-ions concentration being ac. 
curately fixed ? 

In order to find an answer to this question we have a series of 
experiments which yielded unexpected results with reference to the 
influence of the Ca-ions concentration on the lumen of the blood- 
vessels (capillaries). 

Of course the inquiry was begun by repeating GuNzBuRG’s experi- 
ments. A perfusion of the ordinary Rineer’s liquid (NaHCO, 0,02°/,) 
1) Van Paassen, Ned. Tijdschr. v. Geneesk. 65, 2e helft, nr. 17, 1921. 

3) Hameuncer and Brryxman, These Proceedings Vol. XX, p. 668; Biochem. 
Zeitschr. 88, 97, 1918. 

3) Gunzpura, Arch. Néerl. d. Physiol. 2, 364, 1918. 


147 


did not cause cedema, which indeed came forth, when K was left 
out, just as GunzBure has shown. 

Now mixtures were applied of NaCl 0,6 °/, with several quanta 
of CaCl, . 6 aq. The result was that cedema appeared when 
CaCl, .6 aq. 0,003 °/,, 0,005 °/,, 0,006 °/, was applied, but that 7¢ 
stayed awvay when CaCl, .6 aq. 0,007 °/, was used, even when the 
hydrostatic pressure was raised from 35 to 70 em. 

These experiments, therefore, went to show that, contrary to 
GunzBuRG’s opinion, K may be taken from the circulating fluid, 
without evoking cedema’), in other words, that no radioactive sub- 
stance is required to prevent cedema. 

Now it seemed to be interesting to add some K to this circulating 
fluid (NaCl 0,6 °/, + CaCl, .6 aq. 0,007 °/,), which, as has been said, 
does not cause codema. The addition of KCl 0,01 °/, produced 
cedema. It may be concluded, therefore, that the absence of wdema 
on adding KCl in the experiments of GuxzBurG cannot be due to a 
specific Potassium-action. On the other hand, it became rather evident, 
that when a definite concentration of it is present in our NaC]— 
CaCl, mixture, cedema is sure to appear on that account, so that 
it becomes obvious, that the prevention of cedema by the 0,007 °/, 
CaCl, 6 aq. solution is balanced, and even more than balanced, 
(this depends on the amount) by the antagonistic Potassium. 

Now, how are we to account for Gunzpure’s finding that a pot- 
assium-free Rincur’s mixture evokes cedema? It is probably to be 
ascribed to the fact that this circulating fluid contained only 0,02°/, 
of NaHCO,, of which according to Rona and Takanasn’s’) formula 
a large amount of Ca-ions is the consequence. 

A direct measurement of the Ca-ions concentration after BriInKMAN 
and van Dam‘) proved that the Ca-ions concentration used by GunzBurG 
was, indeed, much greater than in the above-named mixture of 
NaCl 0,6 °/, + CaCl, .6 aq. 0,007 °/,. 

We found experimentally that in our mixture NaCl-CaCl,, which 
did not bring about cedema, contained 13 mgrms of Ca-ions per 
Litre, whereas the liquid used by GunzBure contained 20 mgrs per 
Litre, which makes a difference of 35 °/,. 

Now we know that K and Ca are antagonists; the action of K 
being liquifying, that of Ca tending towards coagulation. It is not 


1) It has been shown that, with other kinds of frogs, there are sometimes other 
Ca-ion concentrations needed to prevent cedema. 
2 


2) Rona u. Takanasut, Biochem. Zeitschr. 49, 370, 1913. 
3) Brinkman and van Dam, These Proceedings, Vol. XXII, p. 762. 


148 


surprising, therefore, that the ratio of K- en Ca-ions is of great 
importance for the permeability of the vascular wall. It is evident 
that in an NaCl-CaCl, mixture the constricting power of 13 mgr. 
Ca-ions per Litre is so great, as to keep away cedema. In the 
presence of more than 13 mgr. Ca-ions e.g. 20 mers, as is the case 
in Gunzpura’s tluid, cedema will ensue, if not a certain amount of 
K is added to counteract their effect. A similar phenomenon appeared 
in the case of the kidneys viz. that an excess of Ca-ions content of 
the circulating fluid produced permeability of the glomerular epithe- 
lium for glucose’). The same thing was found by Brinkman?) with 
regard to the red blood corpuscles. Likewise Nruscut.osz*) physico- 
chemical experiments demonstrated that the surfaee-tension of a 
lecithin-suspension in NaCl is as well influenced in the same manner 
by too little as by too much Ca. 


We now tried to ascertain, whether cedema would arise when 
using a mixture of NaCl—CaCl, which contained much more than 
0,007 °/, of CaCl,. 6 aq., just as had occurred when the amount 
was 0,006 °/,. 

With a view to this 0.01°/, CaCl, 6 aq. (instead of 0,007 °/,) was 
dissolved in NaCl 0.6°/,. We expected cedema to come forth. It did 
not come forth, though, which was owing to a quite unexpected 
phenomenon: the perfusion of the liquid through the vessels stopped 
abruptly. It could not be restored even through a considerable rise 
of the hydrostatic pressure. When the same result was obtained 
several times running, also with higher Ca-ions concentrations *), 
further experiments concerning the influence of a higher Ca-ions 
concentration on the producing of cadema had to be relinquished, 
and vascular contraction was supposed to come into play. 

Now the assumption was warrantable that the vascular contraction 
(spasm, tonus) would disappear on addition of K. It appeared, indeed 
that when to the circulating fluid (NaCl0,6°/, + CaCl, . 6 ag. 0.01 °/,) 
0.01°/, KCl was added the perfusion of the liquid was restored again. 

We are justified in concluding from this that when, in a system 
Na -+ Ca, the Ca-ions concentration is higher than agrees with CaCl, . 
6 aq. 0.007 °/,, a constricting influence is exercised on the vessels, 
which may be counteracted by K-ions. This action seems to be 
reversible; it may be repeated several times. 


!) Hampurcer u. Brinkman, Biochem. Zeitschr, 95, 101, 1919. 

2) R. BRINKMAN, Broch. Zeitschr. 95, 101 (1919). 

5) Neuscutosz, Piltiger’s Archiv f, d. ges. Physiol. 181, 17, 1920. 
‘) More about this in a subsequent publication. 


149 


In correlating this result with the well-known observations of 
Curari and Januscnke’), according to which the process of conjunctival 
inflammation may be arrested by instillation of a CaCl,-solution, we 
are led to suppose that a definite concentration of Ca-ions exercises 
a constricting influence upon the vessels and at the same time a 
coagulating action upon the vascular wall. It appears then that both 
these actions are neutralised by K. 

That the contracting and the coagulating action may coincide, 
is substantiated by the observations on. the influence of oxygen. 
Sfverini’) found that oxygen brings about contraction of the vessels; 
while GunzpurG?), reports that a potassium-free Rineer’s mixture, 
which in other cases always caused cedema, did not cause it when 
the mixture was saturated with oxygen. From this it seems probable 
that vascular contraction coincides with decrease of permeability of 
the vessel-wall not only with a definite concentration of Ca-ions, 
but also under the influence of oxygen. 

As regards the inhibition of vaseular constriction through the 
addition of KCI to the mixture NaCl 0,6°/, + CaCl,.6 aq. 0.01°),, it 
appears that the minimal required concentration of KCl is about 
KCI 0,004 °/,. 


SUP MM ACR. Y. 


The described researches, of which a detailed report appeared 
in the Biochemische Zeitschrift*), may be summarized as follows: 

1. When perfusing the frog’s leg with an aqueous solution of 
NaCl and CaCl,, potassium may be absent in the circulating fluid, 
without cedema being evoked. The circulating fluid, however, should 
contain a definite concentration of calcium-ions. NaCl 0.6°/, CaCl, . 
6 aq. 0.007°/, will serve our purpose here. When using CaCl, . 6 aq. 
0.006°/, cedema will arise. This will occur also when to the first- 
named mixture 0.01°/, KCl is added. This phenomenon finds an 
explanation in the fact that the coagulating action of the Ca-ions is 
counteracted by the antagonistic K-ions. 

2. That Gunzpure wanted potassium in his solution to prevent 
oedema is to be ascribed to the fact that he used an excess of cal- 
cium-ions. The arrest of cedema in Gunzpura’s experiments is, 


) Cutart u. Januscake, Arch. f. exper. Pathol. u. Pharmakol. 65, 120/126, 1911. 

2) Luiat Sevérint, ,Ricerche sulla innervazione dei vasi sanguigni’. Perugia 
Boncompagni et Cie (See Bayuss: ,Principles of General Physiology”, 1915, p. 534. 

3) Gunzpure, |.c. 

4) Rupotr J. Hampurcer, Bioch. Zeitschr. 129, 158, 1922. 


150 


therefore, not owing to a specifically radio-active potassium-action 
but only to the long known potassium-caleium antagonism. 

3. The influence of the K-ion concentration upon the permeability 
of the vessel-wall (mentioned sub 1 and 2) coincides with an 
influence upon the capillary lumen. A perfusion of the vascular 
system of the frog with a mixture of NaCl 0.6 °/, +CaCl, .6 aq 
0.01 °/, produces so considerable a constriction of the vessels that 
no fluid can pass through any more. When to this mixture a little 
KCl, say, 0.01 °/, KCl is added, the vessels dilate and the fluid 
runs on as before. This process is reversible. 

4. The parallelism of decrease of permeability and of constriction 
of the vessel-wall manifests itself not only under the influence of 
Ca-ions, but also under that of oxygen. 

5. In a quantitative determination of the dilating and constricting 
action of pharmaca after TreNxpeLENBURG, due regard should be 
paid in future to the ratio of Potassium- and Calcium-ions in the 
circulating fluid. 

Irom the Physiological Laboratory of the 

5 March 1922. University of Groningen. 


ERRATUM. 


In these Proceedings of June 1912 (Vol. XV), p. 276, Table II, 
column 5, line 12 from the bottom to replace the there printed 
number 1.18908 by the number 1.69487. 


KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN 
TE AMSTERDAM. 


PROCEEDINGS 


VOLUME XXV 


Nes. 5 and 6. 


President: Prof. F. A. F. C. WENT. 
Secretary: Prof. L. BOLK. 


(Transiated from: ‘‘Verslag van de gewone vergaderingen der Wis- en 


Natuurkundige Afdeeling,”’ Vol. XXXI). 


CONTENTS. 


H. ZWAARDEMAKER: “On the Alpha-automaticity of the Autonomous Organs”, p. 152. 


C. E. B. BREMEKAMP: “Further researches on the antiphototropic curvatures occurring in the 
coleoptiles of Avena”. (Communicated by Prof. F. A. F. C. WENT), p. 158. 


R. WEITZENBOCK: “Ueber Wirkungsfunktionen”. (Communicated by Prof. L. E. J. BROUWER), p. 166. 


]. W. JANZEN and L K. WOLFF: “Studies on the bacteriophagus of D'HERELLE”. (Communicated 
by Prof. C. EYKMAN), p. 171. ad 


A. W. K. DE JONG: “The Biscoumaric Acids”, p. 175. 


G. HERTZ: “On the Excitation and lonization Potentials of Neon and Argon”. (Communicated by 
Prof. P. EHRENFEST), p. 179. 


C. A. H. VON WOLZOGEN KiiHR: “On the Occurrence of Sulphate-reduction in the deeper layers 
of the Earth”. (Communicated by Prof. G. VAN ITERSON Jr.), p. 188. 


E. VAN THIEL: “The Influence of a Catalyst on the Thermodynamic Quantities Regulating the 
Velocity of a Reaction”. (Communicated by Prof. J. BOESEKEN), p. 199. 


J. BOESEKEN: “The Dislocation Theory of Catalysis”, p. 210. 

W. E. DE MOL: “The disappearance of the diploid and triploid magnicoronate narcissi from the 
larger cultures and the appearance in their place of tetraploid forms”. (Communicated by Prof. 
G. VAN ITERSON Jr.), p. 216. 

L. J. SMID Jr.: “Numbers of Circles Touching Plane Curves Defined by Representation on Point 
Space”. (Communicated by Prof. HENDRIK DE VRIES), p. 221. 

A. F. HOLLEMAN: “Monochloro-trinitrobenzenes”, p. 223. 

A. A. WEINBERG: “On Respiratory Oscillations in the Galvanogram of Man”. (Communicated by 
Prof. E. D. WIERSMA), p. 225. 


10 
Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Physiology. — ‘On the Alpha-automaticity of the Autonomous 
Organs.” By Prof. H. ZwaarDeMaker. 


(Communicated at the meeting of June 24, 1922). 


In the organism there are some organs which perform automatic 
movements and whose movements are continued also in parts that 
have been isolated from the body. Without any outward stimulation, 
simply by watching those parts we can follow up the continuation 
of this action in its causal and conditional relations. The type of 
such an organ is the heart. It is the musclecells themselves that 
pulsate, from the earliest embryonal existence up to death. Such a 
pulsating heart-cell is comparatively a simple system of phases, *) 
which, if the nucleus is left out of consideration, is made up of the 
following components: 1s*. 7 ions, H, OH, Na, K, Ca, HCO,, H,PO, 
(resp. HPO,); 2™4. 2 lipoids, cholesterin and lecithin; 3'4. a carbo- 
hydrate, glycogen, which is alternately combined with phosphoric 
acid and isolated from it again; 4". oxygen; 5. proteins and 
water as a solvent. The absolute quantity of every component exerts, 
according to the rules of the equilibrium of the phases, an influence 
upon the whole. Influence may be exerted, a component may even 
be given a certain concentration, by surrounding the cell with a 
nutrient liquid composed for the purpose. In so doing substitution 
appeared to be possible. Na may be replaced by Li or by highly 
purified Cs; K by all radio-active elements’); Ca by Sr and Ba; 
lecithin by sodiumoleonate. Besides the absolute quantity also the 
mutual relations carry weight, notably H:OH, H: HCO,, K : Ca. 
Such interrelations must keep within certain bounds. To test this 
various qualities of the function may be considered: first of all the 
so-called tonus-condition, i.e. the degree of continued contraction 
between the limits of atony and maximal tonus; next the excitability 
in the several intervals of a period; lastly the automatic movement 
itself. Now granting the conditions of the system to be so regulated 
that the bounds we alluded to, have been kept in view, and each 

1) H. Zwaarpemaker, Erg. des Physiol. Bd. 5. p. 135. 1906. 

2) H. Zwaarpemaker, These Proceedings Vol. XIX, p. 633. (1916). 


153 


of the three fundamental manifestations, i.e. tonus, excitability and 
automaticity persist freely, two sorts of automaticity can be elicited 
by superadding successively the several radioactive elements to 
the nutrient liquid which surrounds the cells. Two sorts we say, 
because there are two groups of radio-active elements, which thus 
far I have been able to use as medium in the solutions of Ringer 
or Tyrope to substitute vice versa: 1st. an «-group: uranium, 
radium, emanation, polonium, thorium, 2™¢ a @-group: potassium, 
rubidium. 

We shall now discuss the points of distinction and of agreement 
between these alpha-, and beta-automaticities. 

The principal feature of an automatic, periodic movement is its 
tempo, which in its turn depends again on the so-called refractory 
stage inserted into every period. Now this tempo is determined by 
the amount of radio-activity for the alpha-group, as well as for the 
beta-group. A minimum amount is required for the movements to 
reveal themselves at all, and a maximum quantum that should on 
no account be surpassed. This allows a certain latitute for dosages, 
which is narrow for the alpha-, and broad for the beta-group. 

Somewhere in this latitude there is a point of greatest frequency, 
the optimum. This point being established for the two sorts of rayers, 
-the frequencies will be the same for either group. 

Such an investigation evidently requires a constant temperature. 
It is also clear that, when the temperature is variable the two 
determining factors: amount of radio-active matter and degree of 
the temperature, may cooperate or counteract each other. It has 
already been shown that there is a law, which determines these 
relations, but I do not intend to enter into it here. Now, when both 
for potassium and for uranium the optimum doses have been found, 
which yield the highest frequency, the frequencies for potassium- 
and for uranium-automaticity are equal. This is instanced in Fig. 1. 
In the centre the potassium-beat is shown, separated to the right 
and to the left by a standstill from two other pulsations; these two 
other pulsations represent the paradoxical phenomenon appearing 
when passing from perfect potassium-dosis to a perfect uranium- 
dosis, and conversely '). To the right and to the left the uranium- 
beat can be observed. Its frequency does not differ from that of the 
automaticity in the centre of the figure. 

Another property the two automaticities have in common is a 


1) These Proceedings Vol. XIX, p. 1043, (1917) C.R. Soc. de Biol. t. 84 p. 704. 
Paris 1921. 
10* 


154 


similar need for radio-activity in the several subdivisions of the 
heart. This is seen best when passing from a perfect uranium-dosis 


nn 


nO 


H Hi slits iy 


Fig. 1. 
Frog’s heart Kronecker’s canula 14° C., red light. 


Transition from a circulating fluid with 25 mgr. uranylnitrate to another with 
300 mgr. potassiumehlorid per litre, and then back again to 25 mgr. uranylnitrate. 
The transitions generally took place resp. 40 and 60 seconds before the paradox- 


ical standstills, indicated in the figure by a white line. Potassium pulsation in the 
1 


centre. Time !/, min. 

to a perfect potassium-dosis or the reverse with a simultaneous 
registration of the sinus, atrium, ventricle. If no conductive disturb- 
ances occur, it will be seen that the three divisions of the heart 
will stand still and resume their beats at the same moment with 
automaticities of their own. This is illustrated below in fig. 2 for 
an eel-heart in situ, which was perfused first with a uranium-liquid 
and at a moment designated in the time-line by S witb a potassium- 
liquid, 

The phenomenon, instanced in fig. 2 requires, however, accurate 
dosage of uranium as well as of potassium. It would not be surprising, 
if inaccuracy in this respect should engender dromotropism. 

A third property the two automaticities have in common is 
the self-regulation after extrasystole, for @-conditions as complete as 
for the p-conditions. 

The fourth common property is the initial similarity of the alpha- 
and the beta-electrogram, though I must admit that afterwards a 
difference may come forth through secondary influences *). 

Only in adventitious respects do the two automaticities differ. 

Of the greatest importance in this respect is the tonicity of the 
heart. The conditions determining the auto-tonus of the cardiac 
muscle are: 

1) Klinisehe Wochenschrift Jahrg. [I N® 12 (or Diss. H. Stoorr, Utrecht 
4 July 1922). 


155 


a. the number of calcium-ions placed or not placed over against 
univalent-ions. 


= 


the number of H-ions. 


2 


the amount of light incident upon the heart, especially in the 
presence of a fluorescent substance. 


LRN ee beeen en ee NY 


“ous 


Fig. 2. 


Eel’s heart in situ. Perfusion from vena cava, first with a circulating fluid, 
containing 15 mgr. thorium-nitrate per litre, then with a circulating fluid, containing 
100 mgr potassium-nitrate. 1 sinus, 2 atrium, 3 ventricle. Time in sec. At S 
transition from one fluid (thorium-beat) to the other (potassium-beat). Only in the 
ventricle a light tonus is noticeable during the thorium-beat. It has disappeared 
already for the greater part in the first beat performed by the heart during the 
paradoxon. 


When applying uranium as an a-rayer each of the three above 
conditions is modified. Sub a undergoes a change because over 
against the caleium-ion not only univalent ions are placed, but 
also uranyl. Sub 6 is modified, because a solution of urany|-salt 
causes a small increase of H-ions in Ringer’s solution. True, this 
factor may be eliminated by the addition of a trace of CaCO,, but 
let it be supposed that this did not take place. Sub ¢ has been 
modified, because in the organ perfused with a potassium-fluid the 
incident light has only an inappreciable influence unless its strength 
be enormous, while in the presence of a fluorescent uranium-liquid 
also ordinary light will show its tonic action. 

It will, therefore, be considered quite rational that in fig. 1 the 
bases of the uranium-elevations are not so low as those of the po- 
tassium-elevations. When thorium is substituted for uranium the 
phenomenon is less pronounced, still, it is certain that even then 
the tonus is not quite absent, 


156 


With emanation-beats*) and with pulsation evoked by outside 
radiations with polonium, there is often some increase of tonus, 


Fig. 3. 
Frog's heart, Kronecker’s cannula. 

Deprived for some hours by potassium-free perfusion of diffusing potassium 
and of part of the depot. Then pulsating during the night with 100 mgr. of potas- 
sium-chlorid per litre. Next morning standstill with potassium-free Ringer’s mixture. 
Recovery of pulsation due to omnilateral polonium radiation. At the beginning of 
the curve the polonium was taken away. 

Nearly half an hour later the polonium-beats cease. They had caused no increase 
of tonus worth mentioning. 


which need not surprise us if we consider what has been stated sub a, 
Increase of tonus, however, is not a typical feature of alpha-auto- 
maticity, since it can exist without this increase when it is-brought 
about from the outside by polonium-radiation. This is illustrated in 
Fig. 3’). A heart that after cautious, prolonged perfusion with pot- 
assium-free Ringer’s solution, had been deprived of a considerable 
portion of its potassium depot, continued pulsating for a Jong time 
also when subjected from the outside to omnilateral polonium-radi- 
ation. These pulsations oecur without additional increase of tonus. 
The polonium is taken away at the beginning of the figure. 

Besides in the tonus-condition, the two automaticities are also 
distinguished in the relation of the regularly pulsating hearts to the 
action of the constant current, to the alternating current and to dia- 
thermy. These distinctions have been described by Dr. DEN Boxrr *) in 
his Thesis, so that I will not revert to them. 


1) ZWAARDEMAKER and T. P. Feenstra, C. R. Soc. de biologie, t. 84, p. 377. 
Paris 1921. Zwaarpemaker, Klin. Wochenschr. Jabrg. I, N°. 11. 1922. Arch. 
intern. de Physiol. vol. 18, p. 284, 1921. 

2) Another instance is given by ZwaarpemAKeR and G. Gruss, Arch. néerland. de 
physiol. t. 2, p. 502, 1918. 

3) M. pen Boer, Dissertation. Utrecht 1 Maart 1921. 


157 


The heart has served us as a type of the two antomaticities; the 
natural one depending on the radio-activity of potassium, or rubidium, 
and the artificial one, that can be evoked by the radio-activity of 
uranium, thorium, ionium, radium, emanation. In quite the same 
way there is a mutual resemblance between the alpha- and beta- 
automaticities of the gut and the uterus. 


Botany. — “Further researches on the antiphototropic curvatures 
occurring in the coleoptiles of Avena.” By Dr. C. E. B. 
Bremekame. (Communicated by Prof. F. A. F. C. Wenr.) 


(Communicated at the meeting of May 27, 1922). 


As I have shown in my former communication’), the conditions 
under which the coleoptiles of Avena produce an antiphototropic 
curvature, may be summed up in this way: 

1st. At the end of the one-sided illumination the rate of growth 
should have about the same value at both sides of. the coleoptile?). 
This result is only to be obtained with light of rather strong inten- 
sity. If this is provided for, the product of the intensity and the 
exposition-time should exceed a certain value. 

2nd. After the close of the illumination, there should be a more 
rapid increase of the growth-rate, in the side that has received the 
greatest quantity of light. In this way it should reach here a higher 
value. 

An explanation of the way wherein a difference in the rate of 
increase may come about, was given in my paper entitled: “Theorie 
des Phototropismus”’*). After a previous diminution in consequence 
of the illumination, the rate of growth after some time increases 
again. This process commences probably the sooner, according as 
the diminution has -been the greater. In this way the increase of 
the growth-rate in the side which has received the greatest quantity 


!) C. E. B. Bremexamp. On antiphototropic curvatures occurring in the coleo- 
ptiles of Avena. Proceedings Kon. Akad. v. Wetensch. te Amsterdam. Vol. XXIV, 
p: LA7ach9R1: 

2) In my previous work in stead of the expression “the rate of growth at the 
end of the illumination” I used the ampler expression “the rate of growth 
belonging to the grade of sensibility existing at the end of the illumination”. In 
this way I reckoned with the possibility that it would give a latent period between 
the phototropical reaction i.e. the change of the rate of growth, and the absorption 
of the light with its influence on the sensibility. However, a critical examination 
of the literature on this subject, has convinced me that the evidence in favour of 
the existence of this latent period, is not conclusive. The investigations of Bose 
and others have made it very probable that the reaction follows the illumination 
almost immediately. 

5) (C. E. B. Bremexamp. Theorie des Phototropismus. Rec. d. trav. bot. Néer- 
Jandais Vol. XV. p. 123. 1918. 


159 


of light, may gain an advantage of that in the other side. This 
advantage will be the greater, according as there lies more time 
between the moment whereon the growth-rate in the anterior side 
has reached its lowest value, and the moment whereon this is the 
case in the posterior side. If it is sufficiently great, the rate of growth 
in the first-named side with the aid of it will reach at the end of 
the illumination or shortly afterwards a higher value. In any case the 
exposition-time should be long enough that an advantage of sufficient 
extent may be gained. 

However, in my previous communication I showed that an anti- 
phototropic curvature may come about also, if the expositiontime 
is very short. As in this case the explanation given above naturally 
fails, 1 suggested that the theory of Bosk') might give us here the 
clue to get out of the difficulty. 

According to this theory, a disturbance of equilibrium in the 
organism generally manifests itself in a local contraction (the direct 
effect) which is accompanied by an expansion in the adjoining tissue 
(the indirect effect). In the latter, the turgescence would be heightened 
by the water expelled from the contracted portion, and accordingly 
a temporary enhancement of the growth-rate would be the result. 
In this way a normal curvature in one part of an organ would 
always go together with an antitropie one in the adjoining region. 
Only if an inerease of the rate of growth in that part, should be 
impossible, the antitropic curvature would remain out. In our case 
then, the origin of the antiphototropie curvature in the tip of the 
coleoptile might be connected with the origin of a normal photo- 
tropic curvature in the basal part. 

To test the correctness of this supposition, | made a number of 
experiments wherein the phototropic reaction of coleoptiles exposed 
in the whole of their length, was compared with the reaction of 
coleptiles illuminated at the tip only, or illuminated also in the 
whole of their length, but after an exposition of the basal part to 
a two-sided illumination of rather great strength. 

Before I enter into the details of these experiments, I will give 
a survey of the results which previous investigators have obtained 
in their researches on the influence of an illumination of one part, 
on the phototropic reaction of another. 

First of all then, we have to consider the experiments on photo- 
tropism made by Bosr’) himself. They are rather few in number, 

1) J. G. Bose. Plant Respose. London 1900. 


2) J. CG. Bose assisted by Jyotiprakash Sirear. The transmitted effect of photic 
stimulation. Life Movements in Plants. Calcutta 1918/19. p. 362—3877. 


160 


and form only a subordinate part in the general frame of his work. 
His experimental objects were seedlings of Setaria and roots of 
Sinapis. 

The choice of the  first-named object is not very happy, as the 
direct effect of the exposition of the coleoptile is not outwardly 
visible, and its existence therefore, as yet purely hypothetical. The 
indirect effect consists in an antitropic curvature of the axis. This 
curvature which appears almost immediately, is followed in about 
25 minutes by a normal one. The latter should be the result of 
the propagation of the invisible direct effect. An illumination of 
the growing region gives a normal curvature. 

That the antitropie curvature of the axis occurring with an 
exposition of the coleoptile should be the indirect effect of this 
illumination in the sense of Bosr, is possible. It should be remarked 
however, that it is not proved. As yet, we don’t know with 
certainty, if in this case the direct effect consists really in a 
contraction, as no sign thereof becomes outwardly visible. 

The roots of Sinapis show a negative phototropism. At least this 
is the case, when both the tip and the growing region are exposed 
to the light. The curvature appears in the growing region, the tip 
always remaining straight. An exposition of the tip also gives a 
negative curvature of the growing region, but if this part itself is 
exposed to the light, there appears at first a positive curvature 
which only after some time is followed by a weak negative one. 

Bosk considers the negative curvature in the growing region pro- 
duced by an exposition of the tip, as the indirect effect, the direct 
effect as in Setaria remaining concealed. That this curvature is not, 
as in Setaria, followed by a positive one, he explains by assuming 
that the intervening tissue would be practically unable to conduct 
the direct effect. In the case of an exposition of the growing region, 
the positive curvature is considered as the direct effect, whereas the 
negative curvature appearing a little later, is said to arise on account 
of transverse conduction of the direct effect under continued 
illumination. 

However, this explanation is not very convincing. That a neutra- 
lisation of the curvature might come about by transverse conduction, 
is quite conceivable, but how a reversion of the curvature might 
be explained in this way, I fail to understand. Moreover, as a 
conductivity for the direct effect in the longitudinal direction is 
supposed to be absent, it is not readily admissible that is should be 
very efficacious in the transverse direction. Therefore, in this case 


the interpretation of Bost cannot be considered as sufficiently founded. 


161 


The explanations of these negative curvatures given by other inves- 
tigators are, however, hardly more convincing. 

Information about the influence of an illumination of the basal 
part on the reaction of the tip, is to be found in papers by vAN 
DER Wok’), GurTeNnBerG *) and Arisz*), all dealing with the photo- 
tropism of Avena. 

According to vAN DER WOLK the results of an illumination of the 
basal half of the coleoptile on the upper half, is to be seen in the 
fact, that an illumination of 12 MCS gives in these seedlings a 
curvature of the same strength as an illumination of 85 MCS in a 
wholly etiolated coleoptile. This greater curvability of the upper 
half might, perhaps, be explained by assuming that the contraction 
of the tissue in this part was facilitated by the decrease of turges- 
cence in the basal half: the expulsion of the water would find 
here less resistance. 

GUTTENBERG on the contrary, tried to show, that the curvability 
of the tip of the coleoptile is not altered by an illumination of the 
basal part. In his experiments three sets of seedlings were compared. 
They were all illuminated unilaterally with 22,2 or 33,3 MCS; but 
in the second and third set the basal part was exposed previously 
during one hour to an iilumination with 11,1 MC; in the second 
set the seedlings rotated during this time round a vertical axis, 
whereas in the third set they stood still. In this case the after- 
illumination took place from the opposite side. GurrenBere found 
that the phototropic curvature in the third set was a little weaker 
than in the other two. 

This result seems at first in flagrant contradiction to the statement 
of vAN DER WoLKk cited above, but it should be remembered that in 
the experiments of vAN pEr Wo1k, the light was very strong, and 
the exposition only short, whereas GurrenperG used light of rather 
feeble intensity and a very long exposition. Therefore, in the seed- 
lings of van per WoLK the decrease of turgescence in the basal 
part, might have been greater, and consequently the effect on the 
curvability of the tip more important than in the seedlings of 
GuTTENBERG. This explanation would probably suffice, if there was 
no difference at all between the curvatures in the three sets. Gur- 


1) P. C. van per Work. Investigations of the transmission of light stimuli in 
the seedlings of Avena. These Proceedings, Vol. XIV, p. 327. 

2) H Rirrer von Gurtenserc. Ueber akropetale Reizleiting. Jhrb. f. wis. Bot. 
Bd. 52 p. 333. 1913. 

3) W.H. Arisz. Untersuchungen tiber den Phototropismus. Rec. d trav. bot. 
Néerlandais. Vol. XII p. 44. 1915. 


TENBERG stated however, that the curvature in the third set was 
smaller than in the other two, and explained this discrepancy by 
assuming a propagation of the basal curvature to the tip. In my 
opinion it might have ifs cause in the circumstance, that these 
seedlings were already slightly curved at the moment of the after- 
illumination. If this had been the case, the tip would have received 
here a smaller quantity of light and this moreover partly under a 
less favourable angle than in the other sets, and consequently, the 
phototropic curvature would not have attained the same value. It 
should also be mentioned, that a repetition of these experiments by 
Arisz (le. p. 105) gave only doubtful results, the sources of error 
being very great. In any case, we dare not say, that the acropetal 
propagation of the basal curvature has been demonstrated, and for 
the solution of the question, whether an exposition of the basal 
part exercises any influence on the curvability of the tip, the 
experiments are not suitable, the intensity of the light being too 
weak. 

Nevertheless, there are in the paper of GuTTENBERG a few indi- 
cations, which seem to show that the illumination of the basal part 
influenees the curvability of the tip, in the way deseribed by van 
per Work. On p. 341 one may read: “Kin deutlicher Unter- 
schied zwischen den Kriimmungswinkeln der beiden Serien war dabei 
nicht zu konstatieren; doch verhielten sich die allseits vorbeleuchte- 
ten Pflanzen zundechst etwas anders als die verdunkelten. Bei ersteren 
erfahrt néamlich das oberste Drittel der Koleoptile eine etwas 
stirkere Kriimmung als bei letzteren, dafiir ist aber bei diesen die 
Kriimmung bereits. weiter nach unten fortgeschritten”. That these 
differences were only very small (further data lc. p. 437) and quan- 
titatively very different from those observed by van per WOLK, may 
find its explanation, as | have pointed out already, in the feeble 
intensity of Gurrenpere’s illumination. 

Arisz mentions (I. ¢. p. 108), that he has repeated the experiments 
of van per Work, and describes his results in this way: ,,Wohl ist 
in vielen Fallen eine kleine Vergrésserung der Spitzenkriimmung 
beobaehtet worden, welche auch etwas friiher sichtbar wurde, 
aber so eklatant, wie vAN Der Work seine Resultate beschreibt, war 
es nicht’. Arisz therefore does not deny, that the illumination of 
the basal part enhances the curvability of the tip; only he awards 
this influence less importance than van per WoLk does. 

Summing up, we may state that our knowledge of the influence 
which an exposition of the basal part exercises on the tip, is far 
from complete. Moreover, it cannot be said that the available data 


163 


are very valuable for our supposition, that the antiphototropic cur- 
vatures of Avena might find their explanation in this way. 

In the experiments of Arisz (lc. p. 97), the exposition of the 
basal part gave a normal curvature‘), which did not extend itself 
beyond the limits of the part exposed. As the occurrence of an 
antiphototropie curvature in the tip is never mentioned, we must 
assume that under the circumstances of these experiments, the tip 
remained perfectly straight. At first sight, this seems to clash with 
our supposition, but we should remember, that in these experiments 
the tip remained continually in the dark, so that its turgeseence 
underwent no decrease. Now in consequence of this circumstance, 
an increase of the rate of growth might be difficult or even im- 
possible. 

In my own experiments I compared in the first place the reaction 
of coleoptiles exposed at the tip only, with the reaction of coleo- 
ptiles exposed in the whole of their length. The result was very 
clear. Whereas in the first case antitropic curvatures were never 
found, in the second case they could be obtained without difficulty. 

The etiolated seedlings used for these experiments, were planted 
in a single row in oblong zine boxes. Each box got about 15 seed- 
lings, so orientated, that their plane of symmetry was parallel to 
the small side of the box. During the exposition, the boxes were 
placed perpendicular to the rays of light. The seedlings that should 
be exposed at the tip only, stood with their basal part behind a 
screen, so that only 24—3 mm. of the tip protruded. This screen 
was prepared in the following way. A feeble red light was placed 
just in front of the experimental lamp, and the silhouette of the 
coleoptiles caught on a piece of black paste-board standing just 
behind them. The place of the tip was marked thereon with the 
aid of a pencil. Above these marks the paste-board was cut away 
and then the screen pushed 2'/,—3 mm. deeper in the earth. After 
that the box was turned round and the red light removed. During 
the illumination with the experimental Jamp, in this way just 2'/,— 
3 mm. of the tip was exposed. 

The intensity of the illumination was in all experiments 750 MC: 


1) In two experiments out of a very great number, Arisz mentions to have 
obtained antitropic curvatures in the part exposed. In one case (illumination during 
1 minute with 330 MC), the curvatures are stated to have been feebly normal or 
antitropic, in the other case (illumination during 1 minute with 200 MQ), they 
were antitropic or absent. As these cases, however, stand wholly isolated among 
the rest of his results, it seems probable that these antitropic curvatures are due 
to some experimental error. 


164 


the exposition-time 12, 15, 18 and 21 seconds. The temperature 
varied between 15° and 20° C., but in each series of experiments 
it remained nearly constant. After the illumination the boxes came 
on the clinostat. 

With an exposition of 12 seconds (light-quantity 9000 MCS), after 
3'/, hours the coleoptiles exposed in the whole of their length, 
were feebly antitropic (S-shaped); the coleoptiles exposed at the tip 
only, feebly curved in the normal way. 

With an exposition of 15 seconds (light-quantity 11250 MCS), the 
results were nearly the same. 

With an exposition of 18 seconds (light-quantity 18500 MCs), 
after 3°/, hours the coleoptiles exposed totally, were clearly antitropic 
(feebly S-shaped), the coleoptiles exposed at the tip only, nearly 
straight. 

With an exposition of 21 seconds (light-quantity 15750 MCS), 
after 3'/, hours the coleoptiles were all nearly straight. 

The experiment with the exposition-time of 15 seconds, was 
repeated 5 times, always with the same result. That in this case, 
the occurrence of an antitropic curvature at the tip of the totally 
exposed coleoptiles, is dependant upon the exposition of the basal 
part, cannot be doubted. 

The results of the experiments wherein the basal part of the coleo- 
ptiles was previously exposed to a very strong illumination, and 
where, therefore, the unilateral after-illumination of the whole 
coleoptile did not give a normal curvature in the basal part, demon- 
strate the significance of this influence also clearly. 

In these experiments, I compared the result of an unilateral illu- 
mination of the whole coleoptile after a twosided exposition of the 
basal part, with that of an unilateral illumination of seedlings previ- 
ously kept in the dark. During the fore-illumination two screens 
of the same shape were used, one in front of the coleoptiles, and 
one behind them. They were prepared in the same way as those 
used in the previous experiments, the only difference being that in 
this case, the basal part of the paste-board was for the greater part 
cut away. In this way during the illumination, at the tip of the 
coleoptiles a piece of 2'/,—3 mm. remained in the dark. The fore- 
illumination lasted 60 seconds, and during this time, every 10 seconds 
the box was turned round. At the end of the fore-illumination the 
box was turned round for the last time, then the screens ware taken 
away, and the seedlings once more exposed to the same light. This 
time the illumination lasted 12 or 15 seconds. The intensity of the 
illumination was always 750 MC. The result of these experiments 


165 


was, that the coleoptiles, whereof the basal part was previously 
exposed, remained straight, whereas the others showed the usual 
antiphototropie curvature. 

In my former communication I admitted that in coleoptiles previ- 
ously submitted to an omnilateral illumination of a definite value, 
an antiphototropic curvature might, perhaps, be obtained with the 
aid of a rather weak after-illumination. This seems now not very 
probable, as under these circumstances, the occurrence of a normal 
curvature in the basal part, may hardly be expected. Therefore, 
in this case neither of the causes hitherto discovered, by which an 
antiphototropic curvature may be produced, is present. 

The relative importance of the two causes is as yet wholly un- 
known, but that the cause discussed in this paper, must be very 
efficient, follows from the experiments described in my former com- 
munication (l.c. p. 182). The antiphototropic curvatures produced 
by an illumination with a given quantity of light, showed but little 
difference if the exposition-time varied between 1 and 256 or between 
*/, and 192 seconds. Now, as we have seen that with a very short 
exposition-time, the presence of the cause discussed in my earlier 
work, is wholly excluded, we must conclude that its influence in 
the experiments with a longer exposition, was here also rather weak. 


> Ui M M+Ar RK. YY. 


The antiphototropic curvature which appears at the tip of the 
coleoptile of Avena with a very short exposition, does not show 
itself, if the illumination is limited to the tip, or if the basal part 
has previously been exposed to a rather strong illumination. 

Therefore we should assume, that with an unilateral illumination 
of the whole coleoptile, the rate of growth of the tip, is enhanced 
by an influence proceeding from the basal part. This influence must 
be greatest in the side, which underwent the greatest contraction, 
that is to say in the side, which during the exposition faced the 
lamp. The origin of an antiphototropic curvature of this kind is, 
therefore, always connected with the origin of a normal curvature 
in the basal part. 


Mathematics. — ,, Veber Wirkungsfunktionen”. By Prof. R. Wurr- 
ZENBOCK. (Communicated by Prof. L. E. J. Brouwnr). 


(Communicated at the meeting of May 27, 1922.) 
§ 1. Einleitung. 


Bei der Ableitung der Feldgesetze und der Erhaltungssatze in der 
allgemeinen Relativitatstheorie und deren Erweiterungen steht man 
vor folgender Aufgabe: wenn gj, und ¢; die’ Komponenten eines 
Kovarianten Tensors. 2. resp. 1. Stufe sind und 

Ogik O° gik Oe Opi 


Vike. = — », Fike = ——— >. Vie = =). Cie — 1 
“hase On, a On, Oa 2 Fe 02,’ Pins On, Jag ( ) 
gesetzt wird, so ist aus diesen Funktionen eine absolute Invariante 
W «zu bilden. Wig wird dann eine relative Differentialinvariante 


vom Gewichte eins (= eine scalare Jichte) und 


‘[sa=| WV gq de =| ff fw vad du, da,dz,. . (2) 


wird eine absolute Integralinvariante. 
Man nennt Y die Wirkungsfunktion. Bedeutet d eine Variation 
der gi. und g;, so gibt die Gleichung 


afew dx=0 (fir alle dg, und Og;) ee) 


die Feldgesetze. 

Die Frage nach allen Differentialinvarianten zweiter Ordnung der 
beiden Tensonen giz und g; wird zuriickgefiihrt auf die einfachere 
Frage nach allen yanzen, rationalen Differentialinvarianten dieser 
Tensoren. Hierauf gibt ein Reduktionssatz von Ricct und Levi- 
Civita’) die Antwort: man hat alle projektiven Invarianten der 
folgenden 5 Tensonen zu suchen! 


ik - = metriseher Fundamentaltensor 

yi =electromagnetisches Potential 

Rix,23 = (Riemann-Christoffel’scher) Kriimmungstensor . (4) 
Pix) erste kovariante Ableitung der @; 


Pila)(z) == Zweite kovariante Ableitung der gj. 


') Mathem. Ann. 54, (1901), p. 138. 


167 


Die Frage nach allen projektiven Invarianten dieser Tensoren 
bildet ein sehr kompliziertes algebraisches Problem. (Nach dem all- 
gemeinen Endlichkeitssatz von Hinserr gibt es endlich-viele ganze 
rationale Invarianten, durch die sich alle iibrigen ganz und rational 
ausdriicken lassen.) 

Gliieklicherweise ist hier die Sache nicht so trostlos verwickelt, 
indem zwei sehr einschrankende Forderungen gestellt werden: in 
der Einstrin’schen Theorie wird verlangt, dass die Feldgesetze Diffe- 
rentialgleichungen héchstens zweiter Ordnung werden; in der Theorie 
von Wert miissen die aus den Tensoren (4) gebildeten Wirkungs- 
funktionen auch masstabsinvariant sein. 

Wir behandeln zuerst den zweiten Fall. 


§ 2. Die Theorie von Wry. 


In der durch Wry. gegebenen Erweiterung der allgemeiner Rela- 
tivitatstheorie muss die aus den Tensoren (4) gebildete Wirkungs- 
funktion absolut-invariant gegeniiber Masstabstransformationen sein. 
Diese Transformationen sind gegeben dureh 

Op LORE CP nF gt eg Sane uecren (0) 
Ox; 
woraus noch entsprechende Gleichnngen fiir F'j,.3, g'ixz) und P'ii2(3) 
folgen. 

Die Forderung W’ — (fiir alle 2) erniedrigt dann die Anzahl 

5 der Tensoren (4) auf 4+ masstabinvariante Tensoren : 


gik == metrischer Fundamentaltensor (g'i,= 4 ix) 
Fix = electromagnetisches Feld (Gir—Vik) bi 
*Py.a— Richtungskriimmung CUP ep "4 PP iy, aa) 


Bik, « = fikey— (fo pi + fiz Gr +2 fik F2o—Gui far p?9—Guk fia *) i‘ 
(E' ee) 

Der gegeniiber % —WY)q etwas allgemeinere Ansatz I = Wo, 
wobei W keinen Faktor g mehr enthalt, fiihrt weiters auf die 
Gleichung 

2n, + In, + 3n, = 4, 
wobei W ganz und rational vom Grade n,,n,,n, in den /iz, *Fy23 
und Ez, ist. Daher ist n, =O und fiir n, und n, bleiben nur die 
drei Méglichkeiten (2,0), (1,1) und (0,2) itbrig. Man kann dann be- 
weisen'), dass sich unter diesen Annahmen nur die folgenden sechs 
Wirkungsfunktionen ergeben : 


1) R. Werrzenpoéck, Wiener Ber. 129, (1920), p. 683 und p. 697; dito, 130, 
(1921), p. 15. 
11 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


168 


w, i) 2 Sie fik =—2 Given avis te Jagan) 
i 

W, = Silk Vg 

W = py *F ite Im Ee Un! 
Vg ik lm 

WS FM Pye sp 
ik ik,oo 

om — (x eet) Vir 

|| Laat g 

I, — *fik,ln *F ikeim Vg 


Hiezu machen wir die folgenden Bemerkungen’) 
kommen als Wirkingsfunktionen nicht in Betracht, da ib 


identisch Null geben, wie R. Bacn bewiesen 


hat ?). 


(7) 


8 om 
2 Sung as: 
re Variationen 


YW, ist die 


Maxwetr’sche Wirkingsfunktion, bei Wry. mit { bezeichnet*). Auch 


Ww — W*Vyg wird von Wry. verwendet. 
An Stelle von 28, kann man auch die Invariante 
W, = 8h RE SR avae 
verwenden; es ist namlich : 


2s ae a Ey | +B, +78, + %, 


Die Variationen von 8, und W, wurden von W. 


R. Bacn?) berechnet. 


§ 3. Die Theorie von Einstein. 


(8) 


(9) 


Pauni‘) und 


In der E:ystrin’schen Theorie ist 2% — Wg und W ist ans den 
Tensoren (4) zusammen gesetzt: rational in den gjx, ganz und rational 


in den iibrigen vier Tensoren. 


Variieren wir die gi, allein, so bekommen wir die Gravitations- 


gleichungen W*A—0O; die Variation von pm; ergibt di 
nerten Maxwen1’schen Gleichungen »’—0. Dabei sind 
dichten” *) gegeben durch: 


. Ow 0 Ow 0? OW 
Wik — = es + po = 23S 
Ogi Oar Ogik, a Ow. arg O9ik.«p 
5 0s 0 ( os 0? 028 
i - a = => | = 
Op; Oars \ Oi, « + Ox, 00g 0 Gia 
1) H. Weyt, Phys. Zeitschr., 22, (1921), p. 473. 


3) R. Bacu, Mathem. Zeitschr. 9, (1921), p. 124. 
3) H Wey, Raum, Zeit, Materie, 4. Aufl., (1921), p. 268. 


e verallgemei- 
diese ,,T'ensor- 


\ 
iP 


(10) 


(11) 


4) W. Pauti, Phys. Zeitschr., 20, (1919), p. 457; Verhdl. d. Deutsch. Phys. 


Ges. 21, (1919), p. 742. 
5) D. HivBerr, Gottinger Nachr. 20. 11. 1915. 
R. Werrzenpéck, Wiener Ber. 130, (1921), p. 15. 


169 


] 


Berechnet man diese ,,Variations-Ableitungen” und verlangt man, 
dass sie Differentialquotienten von héchstens zweiter Ordnung ent- 
halten, so ergeben sich die drei folgenden Méglichkeiten : 

A. W enthalt die Rjz,.2 linear, keine giz) und keine gaya): 


Waa Algae k wes yetueds)s) se se SE 2) 
B. W enthalt die yyy) linear, keine Rjz3 und keine giz): 

W=LBGnr > Fic Pia: + = »- ~ , (8) 
C. W enthalt keine Ry. und keine pii.,): 

W=CGn. Gi Pie) *- - - .- - (14) 


Wir behandeln diese drei Falle der Reihe nach. Bei A kann man 
zeigen, dass man nur die zwei Invarianten erhalt: 
At—k— Gehry sAa—Ripe ge .'-. . . (15) 
A, ist das von Einstein verwendete R. 
Im Falle B haben wir drei Invarianten: 


i doin : 
B= Wy + Br= Pinay h + Bi=Vviterayiy" 9. (16) 
Die neben B, noch mogliche Invariante 


i 


oe) 
ist mit Hilfe von B, und A, ausdrickbar: 
B,— B= 9) & — Pay P= Pen & PF = —A, (17) 
Komplizierter ist der dritte Fall C. Hier ist die Anzahl der In- 
varianten sehr gross: das Aufsuchen aller Invarianten kommt hinaus 
auf das Bereclnen eines vollen Systems von orthogonalen Invari- 
anien einer quaterndren Linearform g; und einer ebensolchen (un- 
symmetrischen) Bilinearform ¢j;,.). Dies ist eine bisher noch ungeldste 
Aufgabe. 
Wir fiihren einige der einfachsten Invarianten vom Typus C an. 
Enthalt C erstens keine ;(.), so haben wir die einzige Invariante 
C—O — Pi pu apne « « « « « (¥8) 
Wenn C die gi;,) linear enthalt, haben wir zwei Invarianten 
1 O(gi Vo) 
Vg Oi 
Die Wirkungsfunktion C,Vg gibt zu den Feldgesetzen keinen 
Beidrag, da C,g eine Divergenz ist. 
Von den in den ¥; ~ quadratischen Invarianten C’ nennen wir 
nur noch 


C, = Pia) pi p% ’ C=%,)= (19) 


C,=2 (Via ge — gia) pX)) = fxs. « « - (20) 
11* 


170 


Hier ist fj, das elektromagnetische Feld und C,Wq ist die 
Maxwetr’sche Wirkungsfunktion. 

Sind /,(y) Polynome von ¢ (Vgl. (18)) mit constanten Koeffi- 
zienten, so hat die allgemeinste Wirkungsfunktion die Gestalt 


BW=(AMTAMA+ANA+A@F tHE +B: + Og (21) 
C’ bedeutet hier eine ganze rationale Funktion von Invarianten (14). 


Von dieser Wirkungsfunktion ausgehend, waren nun die Feld- 
gesetze aufzustellen. Dies ist bisher nur fiir die einfachsten Invari- 
anten durchgefiibrt worden. 


Bacteriology. — ‘Studies on the bacteriophagus of DHERELLE”’. 
By J. W. Janzen and L. K. Wore. (Communicated by Prof. 
C. Eykman). 


(Communicated at the meeting of May 27, 1922). 
IV. About the relation between bacteriophagus and resistant bacteria. 


D’ Herese tells us in his book that, when a weak bacteriophagus 
is added to a thick emulsion of bacteria, the former will have 
disappeared from the suspension after some time. 

Then he says that the bacteriophagus also seems to penetrate into 
the bacteria, but that, now that the bacilli eould not increase, the 
bacterium resists the bacteriophagus, which is destroyed in vivo. 
We have considered it important to study this phenomon carefully 
once more; for this we have nsed some typhoidbacteriophagi, one 
resistant and one not resistant typhoidstrain out of our collection. 

We have found that the disappearance of the bacteriophagus as 
described by vb’ Here.ie for thick emulsions also takes place in the 
ordinary thin emulsions, this time not of normal but of resistant 
bacilli. 

We have also found that old non resistant bacilli, which are not 
being dissolved by the bacteriophagus in consequence of their age, 
do absorb the latter; in this case however, the bacteriophagus only 
increases when the bacteria multiplicate and so get young again. 

Some of the series of experiments about this subject are as 
follows : 


Series of experiments 1. 


Resistant strain — T 20. Non resistant strain = T Wi. 

Determination of the number of bacteriophagus germs by counting 
the number of islands (on agarplate). 

Bacteriophagus Wi, 

Adding equal portions of bacteriopliagus Wi to equally turbid 
suspension in broth of T 20 and T Wi. 

Number of bacteriophagus germs per eM*. 


| T 20 T Wi. 
Directly | (18 milliard) 18 milliard 
'/, hour 0.6 a OFS 
3/, hour 2.4 a innumerable 


1'/. hours 08 
24 hours 0.02 


” ” 


” 


A second experiment with T(Sm) instead of T (Wi) offered an 
analogous result. 


T 20 T Sm. 
Directly (30 milliard) 30 milliard 
after '/,hour| 1.7 ‘ 4 = 
yl hour ||""4 . 100 - 
», 24 hours} 1.8 5 innumerable 


After a week the number of bacteriophagus germs with the resist- 
ant strain was about the same as the number found after 24 hours; 
with the non resistant strain it had greatly increased. 

We have regularly found the slight increase (in comparison with 
the number after '/, hour and after */,—1 hour) with the resistant 
strain; the explanation seems to us as follows: the resistant strain 
also has some weaker descendants which can be dissolved by the 
bacteriophagus; hence an increase of the bacteriophagus, which is 
now being caught by the stronger brothers. 

We can easily succeed in destroying the bacteriophagus by cul- 
turing three of four times on broth with new bacilli the mixture 
of bacteriophagus-resistant strains in fresh broth. 


I. Ist culture of bacteriophagus germs| 60 milliard per cM3 
2rd i ~ 7 24 - nooo; 
3rd yy » ” V4» » oo» 
Ath’ % ; 3 7H disappeared? 
DEL F 6 7 disappeared 


173 


Il. Ist culture of bacteriophagus germs | 18 milliard per cM3 
2nd ” ” ” 0 02 ” ” ” 
3rd g - i disappeared 


Finally an experiment with old non resistant bacilli. 
A. 14 days old bacilli Sm in broth. 
B. 6 hours old bacilli Sm in broth. 


A. B. 
Directly (30 milliard) 30 milliard 
after '/4 hour4 , 6 ‘ 
after 3/4 ” 2 ” 800 ” 
after 2 ,,32000,, Innumerable. 


Our typhoid bacilli that are resistant by nature to the bacterio- 
phagus do not even lose their resistance after being subcultured 
repeatedly in contradistinction to what b’Hrreiin tells us in his 
book (pag. 67) about the bacilli, who are been made resistant by 
influence of the bacteriophagus. 


V. About big and small islands. 


O. Bam and T. Waranase have said that, in plating a mixture 
of bacteriophagus and bacteriacultures on agarplates, the islands are 
not always equally big, but that sometimes big ones, medium ones 
and small ones are to be found. 

They have tried to cultivate the bacteriophagus of these islands 
purely; they say that they have succeeded in doing this with the 
small islands, not with the big ones however. 

We too had already been struck by this before Bait’s communi- 
cation reached us, and we have tried to isolate these bacteriophagi, 
forming big and small islands, from each other, but we did not 
succeed. We have stated though, that it could not be possible in 
our cases, as a bacteriophagus which exclusively formed big islands 
with regard to one typhoidstrain, made nothing but small islands 
with regard to another typhoidstrain, and as to a third, both big 
and small ones. So we do not believe that Bain’s and Wartanase’s 
explanation is right, but we think the difference in size of the 


174 


islands must be attributed to a difference of virulence as to the 
various strains. Big islands point to a strong effect with regard to 
the typhoidstrain; small ones to a weaker effect. This has also been 
proved by a still to be published investigation of Dr. Kropyeip in 
our laboratory, about staphylococei-bacteriophagi. 

Bacteriophagus Wi always gives both big and small islands with 
regard to T Wi. 

Small and big islands are cultured over separatly 9 times, small 
islands always being used for the series of small ones, big islands 
for the series of big ones in this process. 

The last culture of both always gave a mixture of big and small 
islands again. 

Finally we have tried both bacteriophagii Wi big ‘* and Wi 
small ** as to 4 typhoidstrains. 

With both bacteriophagusstrains we got exactly the same result 
which is only following once. 


1. Clearing. 2. Checking. 3. Islandformation. 


Typhoid 9 +-+++ -f-]--b-- +-+-+-++ very big islands. 
im lS SSe SSF ++++ big islands. 
Sie el = Se +tt+ very small islands. 


» Wi 4++4¢+4+ +-+-++ +++ + big and small islands. 


Laboratorium of Hygiene. 
Amsterdam, May 1922. 


Chemistry. — ‘“Vhe hiscoumaric Acids’. By A. W. K. pe Jone. 
(Communicated at the meeting of May 27, 1922). 


Some time ago’) | communicated that the product of illumination 
of coumarin is not identical with hydrodicoumarin of Frrriag and 
Dyson, as Cuamician and Sinper had thought, but that it must have 
another structure, because when treated with alkalis it does not 
give a mono-basic, but a di-basie acid. 

It is natural to suppose that the product of illumination of coumarin 
is formed from coumarin in the same way as e- and @-truxillie 
acid are formed from the forms of normal cinnamic acid by the 
combination with formation of a tetramethylene ring between the 
doubly bound C-atoms of the two molecules. 

As two molecules of normal cinnamic acid can combine in four 
different ways to a truxillic acid’) also the combination of two 
molecules of coumarin will give four different biscoumarins, which 
will, as the truxillie acids, belong to two series according to the 
arrangement of the C-atoms with unequal (1) or equal (ID) atom- 
groups next to each other in the tetramethylene ring. 


© 0 
HG eis. / 
C,H, GO C,H, CO 
we NA 
“CH CH — CH 


ses 
CH =A 


WEA Win Xe 
Hi, C,H, ‘0 
NAL 
Il. 


— 


Of both structural formulae two different biscoumarins can exist 
according to the situation of the coumarinrings on different sides or 
on the same side of the tetramethylene ring. 


1) These proceedings Vol. XX, 875. 
2) These proceedings Vol. XX, 590. 


176 


To the product of illumination of coumarin one of these four 
structural formulae must be assigned. 

Also another biscoumarin is known, obtained by Kyour T. Strém ') 
by boiling bisecoumaric acid, formed by illumination of coumarie 
acid, with anhydrous acetic acid. This biscoumarin is, as STROM 
already communicated, different from the biscoumarin obtained by 
illumination of coumarin, nor is it identical with the hydrodicou- 
marin of Firrig and Dyson. 

The biscoumarie acid of Srrém is formed from coumaric acid, of 
which no metastable forms are known till now, in a conformable 
way as a-truxillie acid of a@-normal cinnamic acid, and therefore it 
is very likely that this biseoumaric acid will have a conformable 
structure to a-truxillie acid. The properties of this biscoumaric acid 
known at present are in agreement with this, as will be shown. 

The biscoumarin of Strém would then possess the structual 
formula I, the conmarin-rings being situated on different sides of 
the ring. 

To distinguish the different biscoumaric acids I propose to give 
to these acids similar names as to the truxillic acids, and then the 
biscoumaric acid of Srrém must be ealled a-biscoumaric acid, and 
its biscoumarin a-biscoumarin. The melting- at the same time 
decomposition-points of the two substances are the same, viz. 
318° (Srrém stated them to be above .275°); a-biscoumaric acid also 
changes into its bisecoumarin when heated to 250°. The biscoumarin 
obtained by illumination of coumarin might be different from a-bis- 
coumarin by the position of its coumarin-rings situated, on the 
same side of the tetramethylene-ring or it might be one of the two 
other possible biseoumarins indicated by figure II. The first sup- 
position was not very likely, the two biseoumarins showing no 
change when heated at 210° with the acetic acid anhydride, whilst, 
when they bad only a difference in the situation of the coumarin- 
rings with respect to the tetramethylene-ring, a change of one into 
the other was probable. This experiment is, however, not a con- 
clusive proof of a different binding of the coumarin-molecules in 
the biscoumarins. The best way to decide this is to-prepare the acid 
of the biscoumarin, converting it to the dimethylether, and to try if 
through heating with the acetic acid anhydride at 210° an anhy- 
dride is formed which gives a dimethylether of another biscoumaric 
acid. If the two coumarin-rings are situated on the same side of 
the tetramethylene ring, no other biscoumaric acid is formed, whilst 


1) Ber. 37, 1383. 


177 


when they are on different sides, a new biscoumaric acid will be 
obtained. 

The methylation of a-biscoumaric acid by dimethylsulfate gives the 
dimethylester of the dimethylether crystallized into needles, melting 
at 133° and sparingly soluble in ether. On boiling with alkalis 
the dimethylether was obtained melting at 261°—262°. Bertram 
and Kirsten’) found the melting point of this substance, obtained 
by illumination of the methylether of coumaric acid, to be 
260—262?°. 

When the dimethylether is heated with the acetic acid anhydride 
at 210°, the anhydride of the dimethylether of y-biscoumaric acid 
was formed, which crystallized in pretty large bright yellow crystals 
out of the anhydride of acetic acid, melting at 186°--187°. The 
dimethylether itself was obtained in fine needles melting at 234°. 

When the a-biscoumarie acid is heated with KOH the acid corre- 
sponding to 8 cocaic acid was obtained, which separated in an 
ether solution by addition of petrolether in rhomb-shaped crystals 
melting 212°. As it whould be strange to give this acid a name 
connected with coca, I propose to call it $-biscoumarie acid. With 
a similar treatment also the dimethylether of @-biscumaric acid gave 
the same acid, which shows that the methylgroups are split off 
through melting with KOH 

These transformations of the «-biscoumaric acid, respectively the 
dimethylether, are wholly analogous to these of «-truxillie acid. 

The dimethylester of the dimethylether of the biscoumaric acid 
of the product of illumination of coumarin, for which I propose 
the name of A-biscoumaric acid, melts at 112°—113°; the dimethy]- 
ether itself at 134°. 

By heating the dimethylether with acetic acid anhydride at 210° 
and after evaporating the solvent in a glycerine bath at about 130° 
a brown sirup was obtained, which did not crystallize. The acid 
obtained by boiling the sirup with alkali crystallizes out of an ether- 
petrolether solution in fine needles melting at 203°. On account of 
its resemblance in structure with ¢ truxillie acid [ propose to call 
this substance the dimethylether of ¢ biscoumarice acid. This trans- 
formation proves that the coumavrin-rings of the illumination product 
are situated on different sides of the tetramethylene ring and as 
also a-biscoumarin possesses the same situation of the coumarin- 
rings and the two substances are different, 4-biscoumarin must have 
the structure of fig. Il and by the removing of a carboxylgroup 


1) Journ. f. pr. Ch. (2) 51, 323. 


178 


from one side of the tetramethylene ring to another an o-dioxy-é- 
truxillie acid is formed. 

By melting with KOH 2-biscoumaric acid is converted into 
d-biscoumaric acid, crystallizing in needles melting at 157°. 

I hope to make further communications on other possible trans- 
formations of the biscoumaric acids, while it will also be tried to 
obtain them from the truxillic acids, by which the proposed names 
and the structural formulae will obtain more security. 


Laboratory of the Colonial Museum, Haarlem. 


Physics. — “On the Excitation and Ionization Potentials of Neon and 
Argon”. By G. Hertz. (Communicated by Prof. P. Kurenrsst). 


(Communicated at the meeting of May 27, 1922) 


It is known that rare gases and metallic vapours behave in a 
very simple way on collision with slow electrons. Then there can 
be exchange of energy between electrons and atoms only in one 
way, viz. that in which the transferred energy is used to’ bring the 
colliding atom into a higher quantum condition. Hence on collision 
with the atoms the electrons can transfer only very definite energy 
quanta to them, which according to Bonr’s theory, are in direct 
connection with the series-spectrum of the atom. For a great many 
metallic vapours this transition of energy in quanta has already 
been investigated and the relation to the optic spectra has been 
shown. Of the rare gases accurate measurements have only been 
carried out for helium‘), on the ground of which Franck succeeded 
in making the system of the series-spectra of helium complete, and 
in showing the connection between the ortho-helium and the par- 
helium spectrum. Several observations have, indeed, been made for 
neon and argon’), but the resulfs are inaccurate for the greater 
part, and partly in conflict with each other. Besides in the great 
sensitiveness of noble gases to traces of impurities, the excitation 
and ionization potentials of which lie nearly always below that of 
the rare gas, the cause of these conflicting results seems to lie 
chiefly in this that the efficiency of the unelastic collisions in the rare 
gases is much smaller than in the metallic vapours, so that the 
methods which lead to good results for the latter, cannot be applied 
here. In order to attain reliable results, it seemed, therefore, neces- 
sary to me, to refine the methods for the investigation of the quantum 


1) F. Horton and A. C. Daviss, Proc. Roy. Soc. London (A) 95, 408, 1919. 

J. Franck and P. Kyrppine, Zeitschr. f. Physik, 1, 320, 1920. 

K. T. Compron, Phil. Mag. 40, 553, 1920. 

2) F. Horton and A. C. Davies, Proc. Roy. Soe. London, (A), 97, 1, 1920 and 
98, 124. 1920. 

G. Sreap and P. S. Gostine, Phil. Mag. 40, 413, 1920. 

H. C. RenrscHuer, Phys. Rey. 14, 503, 1913. 

G. Désarpin, C.R. 172, 1347, 1921. 


180 


transition of energy between electrons and atoms, and supplement 
it by a method which admits of a clear distinction between light 
emission and ionization also in the case of unelastic collisions of 
small efficiency. 

The methods applied up to now for the study of the quantum emis- 
sion of energy consist in this that either the radiation or ionization 
that take place starting from a definite potential, or the phenomenon 
that the impinging electrons lose energy, is used as a proof of the 
occurrence of unelastic collisions. In this way a curve is obtained 
in which the different steps of energy appear as breaks; an accurate 
measurement of them is often difficult, especially for the higher 
steps of energy. It seemed, therefore, desirable to me to use as 
criterion for the quantum transition of energy a characteristic that 
immediately disappears again when the critical potential is exceeded, 
and consequently causes the separate steps of energy to stand forth 
as sharp maxima. Such a characteristic is the occurrence of electrons 
with the velocity zero. For as soon as an electron possesses exactly 
the energy required for the excitation of a definite quantum transition, 
it may lose all its energy at the collision, and be left behind as 
an electron with the velocity zero. If, however, it possesses a greater 
energy, it retains the rest after the collision, and remains behind as 
an electron with a velocity which, though smaller, is yet different 
from zero. If, therefore, electrons of a definite velocity, are admitted 
into a space in which they collide with atoms of a noble gas, 
electrons of the velocity zero will only occur when the energy of 
the electrons is precisely equal to the work required for the excitation 
of a quantum transition. When, therefore, the number of electrons 
which are left behind with the velocity zero, is plotted as function 
of the accelerating potential, a sharp maximum must be obtained for 
every potential corresponding with an energy-quantum that can be 
transferred at a collision of electrons. In consequence of the inevitable 
distribution of velocity of the electrons it is not possible to determine 
the number of electrons which have rigorously a velocity zero. 
Therefore the number of those electrons the velocity of which les 
below a definite small value (in our measurements mostly 0.2 Volt) 
will be plotted as function of the tension. 

The measurements according to this principle are carried out in 
the following way : 

The electrons emitted by a short incandescent wire D of tungsten 
(Fig. 1) enter the field-free space FR through the gauze JN, after 
acceleration through an electrie field, in which space they collide 
with the atoms of a rare gas. Part of the electrons passes through 


181 


the cylindrical gauze N, after numerous collisions; opposite this 
cm gauze a receiving plate has been adjusted, 
also cylindrical. (The cylindrical arrange- 


uw 


ment of VV, and P appeared to be prefer- 
4 able, though good results were also ob- 


| R N.|P |, tained with an apparatus with two parallel 
i pieces of gauze and a plane receiving plate). 
2 When between NV, and Pasmall retarding 
{ potential is applied, all the electrons, the 
N, ; velocity of which corresponds to smaller 
D potentials, are held back. A certain part 

| of the faster electrons will likewise be 

Fig. 1. retained by the weak counter-field, but 


as appears on closer consideration, this part greatly decreases with 
increasing velocity. The difference between the stream of electrons 
received on the plate with and without the small counterfield, 
therefore, gives a measure for the number of electrons having about 
the velocity zero. In order to be able to measure this difference with 
great accuracy, an arrangement was chosen which rendered it 
possible to insert and cut out the field alternately; the part of the 
potentiometer from which the small counter-potential had been branched 
off, could be short-circuited by a mercury contact in vacuum. By 
alternate reading of the deviation with and without counterfield the 
difference could be accurately read, and an error in consequence 
of a possible change of the zero-point was out of the question. It is 
further possible to render oneself independent of a slow change in 
the emission of electrons of the incandescent wire, by dividing the 
difference measured by the total deviation. For the efficiency of the 
method it is of importance that the metal surfaces should have the 
greatest purity possible, as small impurities can already cause Volta- 
potential differences of the order of magnitude of the small counter 
potential. The copper used had been cauterized with nitric acid 
immediately before the construction and the sealing in of the apparatus. 
The whole apparatus was mounted on a pretty large glass foot, as 
is used for incandescent lamps, so that it could be fused into a 
glass globe without the metal parts being heated too much. It was 
heated at 400° in bigh vacuum for six hours; after this the copper, 
even though it was a little tarnished before in a few places, presented 
a perfectly pure metallic surface. 

In figures 2 to 4 curves are represented as instances of the results 
of such measurements, which refer to neon of a pressure of 
0,51 m.m., to a neon-helium mixture of 30°/, helium and a pressure 


182 


of 0,56 mm. and argon of 0,36 m.m. pressure. Especially fig. 3 
shows the efficiency of the method. In spite of the comparatively 
small percentage of helium, the two first excitation tensions of 
helium, though they lie above the strong excitation tensions of neon, 


| | Neon Helium 


—} ee L Wolk _ 
20 22 4 16 18 20 TTB 


Fig. 2. Fig. 3. 


stand out as two sharp maxima at a distance of 0,8 Volt. These 
maxima were used to obtain the absolute value of the excitation 
tensions of neon, in which the value of 20,45 Volts measured by 
Franck and Knipprnc') for the lowest excitation tension of helium, 
was used as basis. The values thus obtained appeared to be inde- 
pendent to a high degree of the circumstances of the experiment. 

This .method is entirely unsuitable for the measurement of the 
ionization-potential. For then the impinging electron or the electron 
that has been liberated from the atom by the collision can have 
the velocity zero after an ionizing collision, also when the energy 
of the colliding electron was greater than the work of ionization. 
As moreover at first the effect brought about by ionizing collision 
evidently rapidly increases with increasing tension, the curve shows 
no maximum here, but only a rise, which is besides influenced by 
the positive ions, and does not admit an accurate determination of 
the ionization-potential. For this reason the arrangement usual 
with a strong counter-field between N, and P was used for the 
measurement of the tension of ionisation for some measurements ; 
most observations were, however, made according to a new method, 


1) J. Franck and P. KnIpPING, l.c. 


183 


in which a very reliable criterion is applied for the first appearance 
of the ionization. For this purpose a second, very thin incandescent 
wire G of the shape represented in Fig. 5 was placed in the field- 


awe 
srl c.m 
5 
mom Ra — 4 
| 
' 3 
G 
“ates ms (aa Nail 2 
i 1 ieee} ‘ 
| i rgen i 
| easel D F 
OL es =. # aaat j 
10 P & 16 oe 
Fig. 4. Fig. 5. 


free space Ff; the positive end of this wire (on the left side of the 
figure) was connected with the walls of FR, so that the field round 
the wire, which moreover remains restricted to its immediate neigh- 
bourhood on account of the slight thickness of the wire, can by no 
means accelerate the electrons coming from LY. This incandescent 
wire was heated to such a temperature that the stream of electrons 
flowing from the wire to the metal wall, is limited by the space 
charge. So long as the energy of the electrons coming from PD is 
not sufficient for the formation of positive ions, they have no in- 
fluence at all on the amonnt of the stream of electrons issuing from 
G. Nor could a photo-electric effect, if it took place, even apart 
from the fact that it is so small, have any influence on the amount 
of this stream of electrons, limited by the space charge. As soon, 
however, as positive ions are formed, and some of them get into 
the neighbourhood of G’, the space charge is partly annihilated, and 
the stream starting from G suddenly rises. Figures 6 and 7 show 
the results of these measurements in neon and argon. It is seen that 
not even the slightest discontinuity can be perceived in the curve 
when the lower excitation tensions are passed, while at the tension 
of ionisation the stream begins to rise rapidly. To obtain the absolute 
value of the ionization potential, the maximum corresponding to the 
first excitation potential was determined’ at the same time by the aid 

12 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


184 


of N, and P according to the method discussed above, which is 
likewise expressed in the figures. In this it should be taken into 


i] 


Fig. 6. 
account that this maximum slightly differs with respect to the 
tension at which unelastie collisions take place, viz. the amount 
equal to the small counter-potential (here 0,2 Volt). It may also be 
mentioned that the measured stream in these experiments was about 


0 


° 


Fig. 7. 


thirty times the flow of electrons issuing from D, so that in this 
way an accurate measurement of the ionization potential is possible, 
even with an ordinary millivoltmeter. 


185 


Results. Starting from the value of 20,45 Volts for the lowest 
excitation potential of helium, two rather pronounced excitation 
potentials were found for neon at 17,35 and 19,15 Volts, 22,2 Volts 
was found for the ionization-potential of neon; for argon two excita- 
tion potentials were found at 12,25 and 13,7 Volts, a less distinct 
one at 14,7 Volts; the ionization-potential at 16,0 Volts. 

With the very complicated structure of the optical spectrum of 
neon the occurrence of discrete fairly pronounced excitation potentials 
seems surprising at first sight. If, however, the serial scheme of 
neon drawn up by Pascuen’) (fig. 8) is plotted in a scheme in the 
way given by Bone, it is directly seen that the values found are 
in very good harmony with the optical measurement. The term 


2 % 6 13 20 22 vours 
tS 1 
100.000 zob00 veda 166000 182.000 
222 Volk 
oss 
ee I735Vat 
osy™ 
Fig. 8. 


corresponding with the normal state and denoted by me as 0,5s 
has been added in the scheme, the value of this term has been 
calculated from the ionization-potential. This term 0.5 is first of 
all followed by a group of four terms of the type of 1.5.5; these 
lie close together within a region which, expressed in Volts, is 
smaller than 0,2 Volt., and can, therefore, not be separated in 
measurements with colliding electrons. Then follows a group of 2 p 
terms, the greater part of which lies again within 0.1 Volt. After 
this come, about 1 Volt higher, the 3d terms. The other terms 
succeed each other at distances of at most some hundredths of Volts, 


1) F. Pascuen, Ann. d. Phys. 60, 405, 1919. 
12 


186 


so that the methods of the collisions of electrons is not sufficient to 
separate them, only a “continuous spectrum” can be observed. When 
the curve given in fig. 3 is compared with this, the serial system 
is clearly found back in it. The first maximum corresponds to the 
group of the quantum transitions 0.5 s—1,5s, the second to the group 
0.5 s—2p, and then at a distance of 1 Volt follows the spectrum 
of the transitions to higher quantum conditions, which seems conti- 
nuous on account of the small dissolving power. Also quantitative 
the agreement is good, as is seen in fig. 8, where the quantum tran- 
sitions observed with collisions of electrons have been indicated by 
arrows, of which the projection ou the axis of abscissae is equal to 
the observed value of the potentials of excitation resp. ionization. 
It is, therefore, seen that the serial scheme of neon has become 
complete by the addition of the term 0.5s = 179800 + 1000. 
There is no room in this serial system for a resonance-potential 
of 11.8 Volts and ionization-potentials at 16.7 and 20 Volts, which 
values were derived by Horton and Davigs *) from their experiments, 
nor was there any indication at all in my measurements of the 
occurrence of resonance or ionisation at these potentials. On the other 
hand the experiments of the same investigators on excitation of 
light in neon through collision of electrons *) are in good agreement 
with the conclusions whieh may be derived from the completed 
scheme. As can at once be read from the figure, the lines of the 
principal series must first appear alone starting from 19.2 Volts, 
then from about 20.2 Volts the lines of the secondary series must 
gradually begin to make their appearance, while the whole spectrum 
only can be emitted above the ionization-potential. Horron and 
Davies actually found that at 20 Volts only the lines of the principal 
series were emitted, the whole spectrum not appearing before 22.8 Volts. 

It would be of importance to ascertain whether there may perhaps 
be terms for neon that correspond to metastable states, as FRANCK 
has found them for helium and mercury *). To find this out it would, 
bowever, be necessary really to separate the different terms, and 
for this the dissolving power of the method of the collisions of the 
electrons is not yet sufficient. Measurements with the usual arrange- 
ment for showing photo-electric radiation proved, as was to be 
expected, the occurrence of photo-electrically active radiation at 
both the excitation potentials observed. 

As was already stated above, in argon there likewise appear two 

1) f. Horton and A. C. Daviss, lc. 

2) F. Horton and A. C. Davins, Phil. Mag. 41, 921, 1921. 

3) J. Franck, Phys. Zeitschr. 22, 388, 1921. 


187 


excitation potentials (at 12.25 and 13.7 Volts), and a less distinct one 
at 14.7 Volts, which is followed by a series of energy steps which 
has not yet been dissolved. Here too the apparently sharp excitation 
potentials will no doubt correspond with undissolved groups of terms 
lying close together, on account of the complication of the argon 
spectrum. The argon spectrum not yet having been split up into 
series, a comparison is not yet possible. When a similar structure 
is assumed for the spectrum of argon as for neon, then starting 
from the measured values for excitation and ionization potentials, 
the following mean values for the first groups of terms are to be 
expected : 
0.5 s = 1380000 + 1000 
1.5 s — 30400 
2p = 18600 
higher terms < 10500 


The serial terms calculated by Nissen!) do not fit in with this 
scheme. Also the fact that according to Nissen lines of the red and 
the blue argon spectra are considered as members of the same 
series, though the condition for the excitation of the two spectra 
are different, pleads in my opinion against the validity of the terms 
calculated by him. 

For the rest more complications may possibly be expected for 
argon than for neon. The facet found by Pascuen*) that for part of 
the neon series the limits are shifted by a constant amount in 
comparison with the other series, was explained by Grorrian *) by 
the aid of the L-doublet of neon. He has also already pointed out 
that it must be expected for argon thad the multiple M-limits will 
manifest themselves in am analogous way. 


Physical Laboratory of the “N.V. Philips 
Gloeilampenfabrieken’’. 
(Philips Incandescent Lamp Works). 
Eindhoven. 


1) K. A. Nissen, Phys. Zeitschr. 21, 25, 1920. 
2) F. Pascuen, Ann. d. Phys. 68, 201, 1920. 
3) W. Grorrian, Zeitschr. f. Phys. 8, 116, 192]. 


Microbiology. “On the Occurrence of Sulphate-reduction in the 
deeper layers of the Earth’. By C. A. H. von Wotzocen 
Kine. (Communicated by Prof. G. van IrErson Jr). 


(Communicated at the meeting of April 29, 1922). 


§ 1. Introduction. 

The disappearance of organic matter at greater depths in the soil 
has since long occupied the minds of investigators. The difficulties 
associated with their inquiries regard especially that of obtaining 
sterile samples from such depths, which is essential to microbiolo- 
gical inquiry. 

The process of oxidation, which causes organic matter to disappear, 
can be effected by free as well as by combined oxygen. When the 
air is shut off, as is the case in the lower strata, oxidation is of 
course brought about by combined oxygen. 

Now the question is how this process can take place microbio- 
logically. 

The term sulphate-reduction designates the process by which, 
with the exelusion of air, organic matter in the soil is oxidized 
under the influence of combined sulphate-oxygen. This anaerobic 
process is effected by Microspira desulfuricans, discovered in 1895 
by Brrerinck’). It being an exothermic process energy is set free 
through this oxidation, which is utilized physiologically by the 
sulphate reducing spirilla. The rough equation for sulphate-reduetion 
gives the following formula: 

2C...+ CaSO, + H,O —CaCO, + CO, + H,5, 
in whieh C... is the symbol for the source of carbon. 

Mierospira desulfuricans oceurs in the mud of ditches and the 
ooze of the Dutch “Wadden”. The grey, bluish-black to black colour 
of the soils in which sulphate-reduction takes place, must be ascribed 
to ferric sulphid, in which form the liberated hydrogen sulphid is 
combined by iron-compounds present in the soil. 

The occurrence of the sulphate-reducing microbe at the greater 
depths in the terrestrial soil has been less frequently observed and, 


1) Ueber Spirillum desulfuricans als Ursache von Sulfatreduktion. Verzamelde 
Geschriften. 3de deel, pg. 102. 


189 


to my knowledge, statements about it are few and far between. 
JentzscH ') e.g. records that in the deeper ooze-layers of the ocean 
of about 40 m. and more, reduction-processes occur, in which bydro- 
gen sulphid and ferric sulphid are formed, which are ascribed by 
him to decomposition of proteins. It is more likely, however, that 
here also we have to do with sulphate-reduction, since it has been 
proved that this is of frequent occurrence under the circumstances 
alluded to. 

Another statement is given by Eve. Dusois*) who observed the 
transformation of sulphate into ferric sulphid in the lower alluvial 
clay-layers underneath the Duteh Dunes. 

An opportunity to ascertain the occurrence of sulphate reduction 
in deeper layers was offered, when in the autumn of 1921 a number 
of new wells were dug along the Sprenkelkanaal on the source of 
supply of the Amsterdam Dune Waterworks. 


§ 2. How the samples of sand, clay and peat were obtained 
from the well-shafts. 


In connection with the bacteriological sampling it will be well to 
set forth, in principle, the way in which the new wells were sunk. 

A wide iron tube is driven vertically into a dug, shallow cavity. 
The sand is excavated from a greater depth than is at first reached 
by the tube, which can consequently sink gradually deeper. By 
means of a screw-thread one length of tube is screwed on to the 
other, so that a system of tubes is procured of the length necessary 
to reach a certain depth. 

The masses of sand and the occasional lumps of clay and peat 
are removed from the tubes with a so-called ‘puls’’, consisting of 
a hollow iron cylinder of smaller diameter than the tube’s. At the 
lower end it is sharp-edged to facilitate the sinking, while the bottom 
is provided with a valve, opening to the inside. By means of two 
iron bars that are fastened to the edge of the open top-part of the 
cylinder and are suspended on the same point of support, it is 
possible to connect the apparatus to a pulley-block. When moving 
the ‘‘puls” foreibly up and down in the wet mass of sand present 
in the shaft, it is ultimately filled with a pap of sand. The filled 
“puls” is then hoisted up and emptied by overturning it. This process 
of removing the sand from the well-shaft is briefly called ‘“pulsen’’. 


1) Zeitschrift d. Geol. Ges. 1902. 54, p. 144. Cf. Ramann, Bodenkunde, p. 180. 
) Het Leidsche Duinwater. Eene hydrologische studie. 1912, p. 19 en 20. 


190 


§ 3. The examination of the sand- and clay-samples for 
sulphate-reduction. 


From a chemico-biological point of view it is interesting to 
ascertain the origin of the ferric sulphid, which gives a dull-grey, 
greyish blue to bluish-black colour to the soil-samples. The obvious 
hypothesis that the ferric sulphid was formed by sulphate-reduction, 
was in every respect substantiated by the examination of the many 
sand-, and clay-samples procured by means of the “puls”. Thus the 
sulphate reduction in the deeper layers of the earth underneath the 
dunes appeared to be a bacteriological process of common occurrence. 

The demonstration of sulphate reducing spirilla was performed 
after the accumulation-method of Brtserinck, the culture-medium *) 
used being: 


Tapwater, 03 ee on O00 

WEREOINIO: § oo 6 « 0.5 

ASpPaTapiny |) iy coc gee Q.4 

WIONS TEs 6 5 6 0.05 (ov gypsum) 
FesOe: Trade. > i: eee 0.001 


with which sterile stoppered bottles of + 150 ce. capacity were 
filled after infection with a quantity of the sand-, or clay-samples 
under examination. They were filled up to the neck, then cautiously 
stoppered and placed under 25° C. 

Brisertinck?) showed that in this anaerobic procedure Microspira 
desulfuricans is exclusively the causative agent of the sulphate- 
reduction manifesting itself, as appears from the formation of hydro- 
gen sulphid and the black ferric sulphid. 

My enlture bottles showed in every respect the same progress 
of the reduction process, so that hereby the examined sand-, and 
clay-samples gave evidence of the presence of Microspira desulfuricans. 

The material used for infection of the medium was drawn from 
the inner portion of the sand-mass in the ‘‘puls’” by means of a 
sterile spatula, and deposited in sterile wide-mouthed stoppered 
bottles. Directly when the samples were received at the laboratory 
they were subjected to investigation. 

Sterile sampling could be effected to perfection only in clay-, and 
peat-samples. This was performed after Briserinck’s*) method. The 
sample was split in two. From the fracture laid bare, the required 


1) A. vAN DELDEN. Beitrage z. Kenntn. d. Sulfaatreduktion durch Bakt. Centralbl. 
f. Bakt. 2e Abt. 1903. Bd. XI, p. 83. 

3) \erzamelde Geschriften. (Collected Papers) Vol. 4, p. 53. 

3) Verzamelde Geschriften. (Collected Papers) Vol. 2, p 354. Note 2. 


191 


inoculation material was taken by means of a sterile spatula. The 
lumps of clay and peat suited our purpose well, since in the splitting 
the fracture was not contaminated by crumbling particles of the 
edges, which was owing to the solid structure of the samples 
resulting from their humidity. 

The time in which the formation of hydrogen sulphid in the 
culture-bottles commenced was very different for the same inoculation- 
substance and especially for the sulphate reduction it largely depends 
on the number of viable germs present at the outset of the experiment. 

The clay-, and the peat-samples dredged up with the ‘“puls’, 
were derived from the clay-, and the peat-banks underlying the 
dunes. They were all compact masses, in which the original stratified 
structure, arising from sedimentation, had been preserved. These 
clay-, and peat-layers. being all but impermeable to water, their 
inside represents the original bacteriological condition of the stratum, 
from which the sample has been taken. 

The clay- and peat-lumps were on the outside wet and on the 
inside, judging superficially at least, moderately humid. The water- 
content of the clay amounted to about 26°/,; in the clay-samples 
which contained peat in (he stratified structure, the content of 
moisture was considerably higher, viz. about 50°/,. The peat-samples 
exhibited the largest amount of water, viz. rather more than 77°/,. 

The clay- and the peat-lumps varied from very large ones to 
those of the size of a fist and appeared to meet the bacteriological 
requirements in every respect. 

§ 4. Summary of results and observations on the inquiry about 

sulphate-reduction. 


The number of soil-samples of the 9 wells which were examined 
for sulphate-reduction, have been summarized in the subjoined table. 

The quantum of infection-material used for every sulphatereduction- 
test amounted to from 5 to 10 ers. of the soil-sample. After an 
interval of from 38 to 20 days sulphate-reduction revealed itself at 
25° C., which period rose to 5 weeks in the case of the peat- 
sample B 31. 

In every well, even the deepest of 34.50 m. below A.P., we 
chiefly found sand over the whole depth, in which irregularly spread 
lens-shaped clay-, and peat-layers occurred alternately. 

With a few exceptions all the sand- and clay-samples indicated 
in the subjoined table, yielded on examination for sulphate-reduction a 
conclusive positive result. Consequently the dull-grey or grey colour 


192 


of the sand-samples and the mostly blue to bluish-black colour of 
the clay-samples points to prevailing sulphate-reduction. This com- 


B 22 B 24 B 25 B 26 B 27 B 28 B 29 B 30 B 31 


\21.6 M. 35 34 M./35.30 M.| 6.50 M.| 8.00 M. 6.50 | 9.50 M.| 8.00 M. 
10.50 M.}12.50 » |74.00 » 
15.10 » |73.25*)» | 6.00 M.14.00 18.50 » |25.30 » 


17.50 » 6.50 » 16.25 > |32.50 » Lee 
28.50 » 16.50 » |20.50*)» |34.50 » 
32.50 >» 29.00 » |23.I10 » 

34.50 > 


B 22, B 24, etc. = wells. 

The values express in metres the depths below A.P. (= Amsterdam level) 
from which the soil samples have been drawn. 

The figures in italics refer to clay-samples which enclose organic particles 
or peat-layers. 

The figures in ordinary type are sand-samples. 

(*) = no sulphate reduction in culture bottle. 


mences at about 10 m. below the surface (7.5 m. —A.P.)') to = 
37 m. (384.50 m.—A.P.) the largest depth examined here. 

The conditions under which sulphate-reduction appears are: 

1°. Absence of oxygen ’). 

2°. The occurrence of organic compounds. 

3°. The presence of sulphate and the required mineral compounds. 

The first condition, the absence of oxygen, is satisfied in conse- 
quence of the considerable depth below the level of the ground. 

The second condition: the occurrence of organic compounds, is 
fulfilled already to the eye by the peat-sample and also by the 
clay-sample with enclosed peat-layers. That the sand-, and clay- 
samples, which do not enclose immediately distinguishable organic 
particles, also contain organic matter, can be demonstrated chemically, 
by the potassiumpermanganate method. This is conducted as follows: 
The soil-sample is boiled with diluted sulphuric acid and filtered. 
The filtrate is cooled down under the tap; now potassiumpermanganate 
(0.01 norm.) is instilled. The first drops are directly decolorized. 
which is owing to the oxidation of ferro- and mangano-compounds, 


1) The grounds of the wells at the Sprenkelkanaal is lying at 2.5 M. above A. P. 
2) Traces of oxygen are left out of consideration here. 


193 


Then a moment follows in which the colour of the added potassium- 
permanganate disappears only slowly: this is the oxidation of the 
organic matter, extracted by the diluted sulphurie acid, for in a 
drop of this extract, placed on a piece of tilterpaper soaked with 
potassium ferrocyanid no ferro can be demonstrated any more. 

The sand-samples are most often not so rich in organic compounds 
as the clay-samples, which often contain peat. Presumably this 
generates a stronger sulphate-reduction than is possible in the sand- 
samples, and this is probably the reason why clay can be darker 
in colour than sand. 

Van Deven *) has shown that for sulphate-reduction organic bodies 
are required which are easily oxidizable. This justities the assumption 
that in the organic substances, demonstrated by us, there are some 
bodies difficult of oxidation and others again which are easily oxidi- 
zable, which is proved indirectly by the sulphate-reduction that 
manifests itself in the sand-, clay-, and peat-samples. 

Also the 3'¢ condition, the presence of the required mineral 
compounds, was satisfied. In our examination for sulphate only small 
amounts could be demonstrated, which is explained by the disappearance 
of sulphate through sulphate-reduction. 

One of the mineral combinations is that of the insoluble, black- 
coloured ferric sulphid, formed by the iron and the liberated hydrogen 
sulphid, as pointed out already in §3. 

From the foregoing we may deduce that the conditions of 
anaerobic life which we found in the deeper layers of the soil, 
fairly agree with the prevailing sulphate-reduction. 


§ 5. The content of ,,aerobic” and ,,anaerobic” germs of the 
deeper layers of the soil. 


Besides the demonstration of sulphate-reducing spirilla in the soil- 
samples, another question arises, viz. whether they contain other 
germs and whether these belong to the aerobes or the anaerobes. We 
examined the samples: 

B 28 29.00 M — A.P. (clay with peat) 
B 29 6.50 — 10.50 M — A.P. (clay). 
B 31 25.30 M — A.P. (peat). 


The number of germs was ascertained in the way described in 
§ 3. With a sterilized spatula inoculation-material was taken from 
the soil-samples, it was then shaken up in sterile tapwater and 


1) Centralbl. f. Bakt. Bd. XI, 2te Abt. 1903, p. 83. 


194 


subsequently weighed. This material was used for making counting- 
tests by sowing the micro-organisms on nutrient gelatin. The counting 
of the microbe-colonies for the aerobic plate-cultures took place after 
48 and 72 hours, after which there was hardly any increase of the 
colonies worth mentioning. 

The anaerobic culture plates for the counting-tests were made 
after Wricur and Burri’s’) culture method, modified by me. As 
this strictly anaerobie method of cultivation yields very good results, 
it will not be amiss to state our procedure. 

In a glass box closed tightly by a glass stopper with a ground 
rim a smaller petri-dish is placed containing a solidified culture- 
medium on which the anaerobes are sown in streaks. The circular 
open space left round the dish is first stopped up with non-absorbent 
cotton-wool on which a layer of absorbent cotton-wool is laid. The 
latter is soaked with 20 °/, potassium hydrate and finally with an 
equal volume of 20°/, pyrogallic acid. 

Throughout. this procedure the petri-dish remains covered. After 
the cotton-wool has been soaked with pyrogallic acid the dishcover 
is removed, while the glassbox is closed by its cover-glass of 
which the glass-rim is smeared with vaselin. The rim of the glass- 
box may also be shut off with paraffin after the lid has been 
adjusted. In order to facilitate the opening of the glass-boxes, the 
wall is provided with a little hole which is shut off with paraffin 
and is opened again before taking off the lid of the box, in 


Aerobes. Anaerobes. 
Soil-sample. 
number of germs number of germs 
per c.c. of soil. per cc. of soil. 


After 48 hrs./After 72 hrs.| After 4 days. | After 12 days. 


B 28 29.00 M. — A.P. 


clay + peat. 
15400 20000 818 409000 
B29 6.50—10.50M. —A.P. 
clay. 20 130 = | 400 
B 31 25.30 M. — AP. a 7000 103600 | 160000 
peat. 


1) J. H. Wricur. A method for cultivation of anaerobic bacteria. Centralbl. f. 
Bakt. lte Abt. 29, 190!, pg. 61. R. Burri. 2te Abt. 1902. 8, pg. 533. 


195 


order to admit the air. Now the cover of the petri dish is easily 
removed. 

The number of anaerobes was counted in the same way as that 
of the aerobes in the same sample. 

Because we had determined the specific weight of the soil-samples, 
we could establish the number of germs per cc. 

Our results we have tabulated on page 7. 

The time in which the anaerobes yielded a constant number of 
colonies was considerably longer than that of the aerobes. 

It strikes us that the anaerobie test yields a total of germs which 
is much greater than that of the aerobic one, while the amount of germs 
in B 28 and B 31 is much higher than that of B 29. The last- 
named fact is perhaps due to the higher content of organic matter 
in the first two soil-samples. 

For the sake of comparison we may add that in raw water from 
the dunes the number of bacteria per ¢.c. varies in round numbers 


from 400 to 1800. 


§ 6. Jt appears that microbes derived from aerobic and anaerobic 
cultwation belong for the greater part to the facultative anaerobes. 


The number of species of bacteria obtained in the preceding para- 
graph by the method described, appeared to be only small when 
we examined their qualities. Generally the anaerobes and the aerobes *) 
were not identical. The following table shows the number of species 
of microbes we found: 


Soil-sample. Aerobes. Anaerobes. 
B 28 29.00 M. — AP. 2 species 4 species 
B 29 6.50 — 10.50 M — AP. 2 > 1 5 
B 31 25.30 M. — AP. iter es Cte ae 


As to their properties aerobes revealed some resemblance in 
acidformation from glucose, Berlin-blue formation from ferri-ferri- 
eyanid, the formation of hydrogen-sulphid from broth (lead-carbonate 
test), the splitting of aesculin, the formation of katalase, and most 
often in the inability to ferment glucose, to form lipase and diastase. 
Spores were not formed. 


1) Probably B 29 anaerobe and one of the species B 29 aerobe were identic. 


196 


A difference in the properties of the two microbe-groups appeared 
from the following reactions: Anaerobes form nitrite from nitrate 
in a marked degree, indican is split extensively in most cases 
(oxidation of indoxyl to indigo-blue), a moderate amount of invertase 
is formed, a large amount of slime (wall-matter) is formed from 
saccharose. Aerobes lack these qualities. They liquefy gelatin, whereas 
the anaerobes do not. 

My investigation into the properties of the microbes did not put 
me in a position to classify them. 

When examining microbes derived from aerobic cultivation for 
their anaerobic behaviour, it appeared that only B31 grew very 
well without air, those of B28 and B29, however, very badly. 
The occurrence of these aerobes seems to show that presumably 
very small quantities of air are to be found at-larger depths in the 
soil, and that they are carried along with the rainwater that 
penetrates at a very slow rate into the deeper layers of the earth. If 
the layer, as is the case here with clay, is only sparingly permeable 
to water, the dissolved oxygen is allowed to diffuse to the places 
where it is to be consumed. 

The microbes obtained from anaerobic cultivation developed 
enormously when living in air. This appeared conclusively when 
the anaerobic culture-boxes after being opened had been standing 
for some time exposed to the air. Then the microbe colonies grew 
larger and larger in a very short time. These bacteria grew very 
well as aerobes, also on nutrient agar-slants. Tested in this way 
the majority of the isolated bacteria appeared to belong to the 
facultative anaerobes, which is consistent with the occurrence of 
these microbes at greater depths. 


§ 7. Research for some other specific species of microbes. 


We endeavoured to ascertain the occurrence of obligate-aerobic 
nitrifying bacteria and of Azotobacter chroococcum, however, with 
negative result, as could be expected. 

Nor could denitrifying microbes be demonstrated; no more could 
we detect anaerobic butyric bacteria and anaerobic bacteria which 
break down cellulose. 


§ 8. Van pER Sieen’s Manganese-Theory for the oxidation of 
organic matter at greater depths in the soil. 


The problem of oxidation of the organic matter in the deeper 
layers of the earth has been discussed by W. G. N. van Der SLEEN 


197 


in his publication: ,,Bijdrage tot de kennis der chemische samen- 
stelling van het duinwater in verband met de geo-mineralogische 
gesteldheid van den bodem.” The writer says (p. 50) that at such 
a great depth bacterial influence on the oxidation of organic matter 
seems to be ont of the question and he suspects manganese salts to 
act as oxygen-carriers. Further on (pg. 62) the writer says: ,,.... I 
do not think that Microspira desulfuricans occurs at such a depth 
as has to be assumed when ascribing sulphate-reduction only to 
this micro-organisme’’. 

On pag. 51 the author records some experiments which go to 
show that manganese can transmit oxygen from the sulphates to 
an organic compound such as hydrochinon. To conclude from this 
that the oxidation of organic matter at the lower depths in the soil 
could oceur in the same way, seems to me hardly admissible unless 
experimental evidence be brought forward that biological oxidation 
is out of the question. Such evidence has not been produced as yet. 
It may be deemed surprising that the author, who, as appears from 
the passage in his publication that we quoted just now, had taken 
cognizance of the bacteriological sulphate reduction has omitted to 
inquire into it. This is the more surprising since on the ground of 
its anaerobic behaviour Microspira desulfuricans is adapted to living 
at greather depths in the soil. 

The evidence produced by our investigation set forth in the 
preceding paragraphs, by which it has been established that sulphate- 
reduction is of common occurrence at the greater depths underneath 
the dunes, warrant the conclusion that oxidation of organic matter 
can be effected by Microspira desulfuricans, without the additional 
influence of manganese compounds. 


§ 9. The transformation of sulphate in the clay-containing 
soil of the dunes and sulphate-reduction by Microspira 
desulfuricans. 


The “Koninklijke Academie van Wetenschappen te Amsterdam” *) 
has brought forth a report on the question to what the presence of 
so called Artesian water in the dune-soil is due, in a preliminary 
advice from G. A. F. Monencraarr and Kuve. Dusors. In an enume- 
ration of the chemical properties of dune-water the report contains 
the following statement : 


') Verslag v. d. gewone vergaderingen der Wis- en Natuurk. Afd. Vol. XXX, 
p. 212. 


198 


“From the surface downwards in and underneath the dune-masses 
the sulphuric acid content diminishes proportionally to the total 
thickness of the clay-layers oceurring in them, i.e. in proportion 
to the increase of the volume of clay-soil, through which the water 
has percolated downwards. 

This phenomenon is the result of the power of clay-soil to convert 
sulphuric acid and then retain it’. 

In the study by Hue. Dupois*) already quoted above, a detailed 
exposition is given of the transformation of sulphuric acid in the 
clay-layers, which consists in a reduction-process in the presence 
of organic matters, with formation of ferric sulphid. 

It is evident from the foregoing that sulphate-reduction, which 
occurs not only in the deeper clay-layers, but also in the sand-soil, 
is brought about by Microspira desulfuricans. The life of this microbe, 
which is adapted to anaerobic conditions, accounts for the common 
occurrence of sulphate-reduction in the deeper layers of the earth and 
especially in the clay-soil, which generally has a.higher content of 
organic matter. 

So long as the conditions of this typically microbiological process 
are fuljilled, transformation of sulphate into ferric sulphid will 
hereby be generated, to which is to be ascribed the partial or total 
absence of sulphuric-acid salts in deep-dune water. 

Heemstede, February 24 1922. 


1) ,Het Leidsche Duinwater”. Een hydrologische studie, 1912, p. 20. 


Chemistry. — “The Injluence of a Catalyst on the Thermodynamic 
Quantities Regulating the Velocity of a Reaction.” By E. van 
Tuien. (Communicated by Prof. J. BénseKen.) 


(Communicated at the meeting of May 27, 1922). 


According to GutpBerG and Waacr’s hypothesis the velocity of 
reaction in a homogeneous system of constant temperature is equal 
to the product of the active masses of the converted substances 
multiplied by the velocity constant. This constant is, of course, 
variable with the temperature, and dependent on the nature of the 
reacting molecules. The differential equations of G. and W. only 
indicate the number of molecules decomposed in the time unit; they 
do not indicate precisely how the reaction(s) takes place; hence they 
do not show either how the reaction constant depends on the 
nature of tne substances and on the temperature. 

Disregarding Nernst’s formalation, in which the velocity of reac- 


chemical force 


tion is put = a formula that proved untenable, 


chem. resistance’ 
Go.pscumipt’s attempt’) to give an explanation of the nature of the 
reaction constant may be called the first. Starting-point for these 
and following theories were especially two considerations referring 
to bi-molecular gas reactions: 

1. the reaction constant (velocity for concentration = 1) is doubled 
about per 10° of increase of temperature, so long as the observations 
are not too far from room temperature. The number of collisions 
of the molecules is proportional to the translatory velocity, hence 
proportional to i’ 7. The increase of this kinetic energy can, there- 
fore, contribute to a maximum of 2°/, to the increase of.the velocity 
of the reaction found. Hence a deeper insight into fhe nature of 
the reaction than is given by G. and W.’s theory is necessary. 

2. if all the molecules of the decomposed gas were in the same 
state, every collision would be followed by a reaction. Every reaction 
would then take place with the same explosive velocity. This not 
being the case, all molecules are not equally reactive. A fraction of 
them is in a more favourable condition. It is, therefore, possible 
that the velocity of reaction is proportional to the number of these 


1) Diss. Breslau, 1907. Cf. also Topp and Owen, Phil. Mag. 37, 224. 
13 
Proceedings Royal Acad. Amsterdam. Vol. XXV- 


200 


favoured molecules. Whether it is necessary for the reaction that 
two active molecules collide, or whether it is sufficient when one of 
them is active, must for the present remain an open question. 

GOLDSCHMIDT assumed that the velocity of reaction is about pro- 
portional to the number of molecules the translatory velocity of 
which exceeds a definite minimum value. Only these molecules, the 
number of which is given by Maxweti’s law of partition, would 
be active. This restriction to the velocity of translation, is however, 
entirely unfounded; it is on the other hand more probable that 
also the intermolecular and interatomic energies play a part in the 
reaction, if is, therefore, more plausible to assume a threshold value 
also for these energies. 

Kricrr’s theory is of a more exact character; it has, however, 
only been elaborated for the simplest cases, as e.g. the dissociation 
»<—2I, in which the reacting substances are already in atomic 
(active) condition. Traurz gave a more general theory of velocities 
of reaction. Starting from van *" Horr’s reaction-isochore: 
dink — Q , be substituted for i and for 
dT rele k, 

ions 1 


(Qi (Ql Da mn fe dT — =r | c'y dT. 


0 0 


He further assumed that &, resp. £, depends only on the proper- 
ties of the initial resp. resulting substances, and therefore split the 
reaction isochore into two parts, each referring to this. For this it 
must also be possible to split Q, rationally, for which purpose T. 
introduces the conception intermediate substances (whieh have an 
exceedingly short period of existence). In the case of the splitting 
up of 2HTZH, + 1, these intermediate substances might be H- and 
l-atoms. For the decomposition of HI into H- and I-atoms a disso- 
ciation energy is again required, inthe formation of H, and I, from 
these atoms a heat Q, is liberated. It is clear that Q, = Q, —Q,. 
Now all the obstacles to the splitting up of the reaction isochore 
were removed, and the following equation resulted : 

- L 
Boe. = Ev, fev dT) p72. 
dl Rad h . 
0 

By integration and further elaboration Traurz obtained a formula 
which in approximation could be reduced to a considerably simpler 
form, and from which some important conclusions may be drawn: 


Bi. 


201 


Q, 
4,571 T 


while the following form may be derived for the temperature coef- 


ficient of the reaction constant: 
4h 
aE 7 fost 


hl Ain Ts Saf far 
kr, itR a 

From the first of the two equations may be read that in bi-mole- 
cular reactions the velocity is greater, as the Q, is smaller, while 
it follows from the second equation that the temperature coefficient 
increases on increase of the Q,. When, therefore, the same reaction is 
brought about without, and one with exceedingly little catalyst under for 
the rest identical circumstances, the catalysed reaction, which proceeds 
more quickly, will require a smaller heat of activation for its mole- 
cules, and possess a smaller coefficient of temperature than the not 
catalyzed reaction, two conclusions which may be verified experi- 
mentally. 

Briefly T.’s train of thought comes to this that he assumes that 
it is required both on formation and decomposition of molecules 
that they pass into a reactive form (not always atoms) with absorp- 
tion of energy and that on collision of these active molecules the 
reaction always takes place. Van ’r Horr’s reaction isochore being 
the starting point in Travrz's theory, it is comprehensible that the 
stress has been laid on the changes of energy taking place in the 
reaction, and that the importance of the constant of integration is 
not sufficiently brought out. And yet it is clear on some consider- 
ation that the only thing required for a bi-molecular reaction is 
not a collision, but a collision at the right place (perhaps with the 
exception of very simple molecules). This favourable constellation 
which may be expressed in the form of a quantity of entropy, does 
not occur in the reaction isochore. Accordingly in Travtz’s theory 
changes of entropy in the reaction have only been considered in 
so far as the number of collisions are concerned. 

That with by far the majority of the reactions change of the 
internal energy of the molecules is accompanied with change of the 
molecular entropy *), is not sufficiently taken into account in Lrwis’s 
theorie either. There, too, it is assumed that before being able to 
react, every molecule must have a certain excess of energy, called 
by L merement of energy. This increment would be absorbed in 


log k = (25 to 35) — ed | 


kr, 


1) Tres~inG, These Proc. Vol. XXIII, p. 143. 
13* 


202 


the form of infra-red radiation of very definite frequency, which 
radiation is present in the medium in virtue of its thermal condition. 
By the application of Pianck’s law of the normal partition of energy, 
the density of radiation of this frequeney can be calculated at every 
temperature, and from this the fraction of the molecules that are 
in reactive condition. Luwis derives that the increment of energy E. 
is equal to a quantum (of the absorbable type) per molecule. 


— Nh = Vreagents- 


Lewis derives for the constant of reaction of a_ bi-molecular 
reaction : 


— 3 3 == /j) vA PB) kT 
9 WAG NAN eC ( om MV 


in which P, = constant, 7’— absolute temp., n4 and nz = index of 
refraction of the substance A resp. B, and k= gas constant per 
molecule. The formula shows very clearly the rapid increase of & 
on rise of temperature. 

The nearer the value of the critical energy is to that of the 
iInean energy per molecule, the greater will be the number of 
molecules becoming active per second, hence also the velocity of 
reaction, the same conclusion, therefore, to which Traurz came. By 
taking the logarithm of the above formula, and differentiating this 
with respect to time, the following form results: 

dink Nh@a+vg)+%/,RL E41, RT 


dt RT? i 


Of reactions which take place as muchas possible under the same 
circumstances, only more slowly or more quickly (to be realized 
with little catalyst), the quicker reaction must have a smaller 1 
din k 

dt 
become smaller, hence also the temperature coefficient of the reaction 


has 


according to the above, from which it then follows that 


constant, for the temp.coét 


dk dink 
—_—_—_ = __ =1+410——-=1410 
kp kp kydt hg 
Lewis (like Traurz) draws the conclusion that a strongly catalyzed 
reaction will indicate a decrease of the temperature coefficient 
compared with the same reaction weakly or not catalyzed. 
On half thermodynamic. half kinetie grounds Koxnnstamm and 
ScueFFerR have derived a relation between the velocities of reaction 
and the thermodynamic potentials of the substances participating in 


203 


a reaction. Starting from this ScHerrer drew up a simple formula 
which agrees with a formula derived at about the same time in an 
entirely different way by Marce.in, viz. : 


ne ae eB, 
RT 

in which # represents the difference of energy between the inter- 
mediate state which is rich in energy, and the mean condition of 
the reacting substances in the reaction, and 4 is a quantity which 
does not contain constants dependent on the nature of the substances, 
except the difference of entropy. This term takes the effective chance 
of collision into account. It follows from the formula that increase 
of the energy increment diminishes the velocity of reaction, increase 
of the difference of entropy on the other hand increases it. In contra- 
distinction with the formulae discussed before, a catalyst need not 
necessarily decrease the energy increment; it is even possible that 
as a result the energy increment is increased, provided the increase 
of factor 6 more than neutralizes this unfavourable action. The 
increase of the energy increment means fewer active molecules, 
increase of B is equivalent to a more favourable chance of collision. 
It is, therefore, possible that the action of a catalyst would consist 
in this that thongh the threshold of energy should be raised, the 
number of favourable collisions has been so much increased that 
the reaction nevertheless proceeds more rapidly. 

In the not catalysed reaction by no means every collision between 
active molecules: would eventuate in a _ reaction. This is a priori 
sooner to be expected for complicated than for simple molecules; 
instances are, therefore, especially to be found in erganic chemistry. 

From increase of the energy-increment ensues increase of the 
temperature coefficient, hence the catalysed reaction can have a 
greater temperature coefficient than the not catalysed reaction. 
Entirely in contradiction with Travrz’s and Lrwis’s conclusions the 
catalysed reaction can have a temp. coef. and an energy increment 
which are greater than those of the same reaction without catalyst. 

Measurements of the velocity of one and the same reaction between 
complicated molecules with and without catalyst and at different tempe- 
ratures might give a decision in favour of Scurrrer’s theory, if a 
reaction could be found which, catalysed, presented a greater tem- 
perature coefficient than not catalysed. As will be seen in what 
follows, this appeared to be the case in the acetylation of diphe- 
nylamin. 

The reaction was carried out at 0°, 20°, 30°, 40°, and 50° C. 


204 


The excess of acetic acid anhydride was taken so great that the 
variations of concentration of this component could be neglected 
with respect to those of the component diphenylamin. Hence the 
reaction was pseudo-mono-molecular. Many catalysts were tried *) 
before some substances were found which were not paralysed during 
the reaction; they were p. bromo-benzene-sulphonic acid and _p. 
toluene-sulphoniec acid. 

The following tables give the observations from O—50° without 
catalyst. 


temp. 0° 1 mol diph. 121/. mol. anh. temp. 20° 1 mol. diph. 12!/, mol anh. 
t 0/9 converted ms t 9/o converted 
S 2.303 a PRs 
1.— uur ile 0.0048 0.30 uur 0.8 0.0069 
25— = 1.4 0.0031 Ie SO ta 2.4 0 0070 
3.— iy 2.1 0.0031 230! 5 3.8 0.0067 
4.— , 203 0.0025 3.30) 5 5.5 0.0070, 
5.— y 2.4 0.0021 4.30 , 1.3 0.0073 
Gal Se 3.0 0.0021 9.1 


temp. 30° 1 mol diph. 12!/. mol, anh. temp. 40° 1 mol. diph. 12!/2 mol anh. 
K : K 

= 0 poate 

t 0/9 converted 2.303 t /o converted 2.303 

0.30 uur 1.6 0.0127 0.33 uur 2.5 0.0220 
LOlne; 2.8 0.0121 0:58, 4.3 0.0208 
2s 55 0.0123 20 5 8.9 0.0202 
3.— 8.2 0.0124 22590 12.9 0.0201 
4.- y 10.8 0.0124 5.— 21.5 0.€210 
6:05.55 16.3 0.0129 i=" 5 29.0 0.0212 


Taking into consideration that in the first table the converted 
quantities are so small, the most probable values of the reaction 
constants are respectively; 0,0021—-0,0070—0,0124—0,0209 and 
0,0384. 


') Diss. Delft 1922. 


205 


temp. 50° 1 mol. diph. 12!/; mol. anh. 


t 0) converted Se 
0.30 uur 4.4 0.0391 
bik 8.4 0.0381 
2.— » 15.2 0.0358 
Se" hy 22.6 0.0371 
5.— 4 36.1 0.0389 - 
1 — ey 46.5 0.0388 


The reaction constants of the catalysed reactions are recorded in 
the following table: 


p.bromo-benzene-sulphonicac. cat.| p. toluene-sulphonic acid catal 
0.00089 mol. 0.00178 mol. 0.00089 mol. 0.00178 mol. 
| 
0.0018 0.0027 0.0021 0.0024 
0.0102 0.0197 0.0105 0.0134 
0.0243 0.0523 0.0235 0.0340 
0.0598 0.143 0.0558 0.0819 
0.153 0.383 0.123 0.194 


It is remarkable that the activity of the catalyst decreases at low 
temperatures, and becomes about O at O°. At lower temperature the 
catalyst is paralysed, to which we shall revert later on. The energy 
increment can be calculated from two observations by the aid of 


e/a 1 
the formula ne =a(p—7): In the caleulation of the energy- 


1 

increment of the catalysed reactions it should be borne in mind 
that this must not be done in the usual way, if the measured reac- 
tion is a combination of two or more reactions taking place side 
by side’). The hypothesis according to which it is assumed that 
with a small catalyst concentration, the number of collisions of the 
kind as occur in the non-catalysed reaction, remains the same, and 
that only another kind of collisions is added to them, is permissible 
in my opinion. In this case the measured constant of reaction 


1) LacomB.#, Diss. Leiden 1920, p. 80. 


206 


represents the sum of that of the non-catalysed and that of the 
purely catalysed reaction. In order to obtain the constants of the 
purely catalysed reactions, which are recorded in the above table, 
the reaction constants of the non-catalysed reactions must be sub- 
tracted from the measured ones. It has been tacitly assumed, what 
is, indeed, shown by the constancy of the measured reaction con- 
stants, that the two reactions proceeding side by side, are of the 
same order, as otherwise this operation is not allowed. 


es | 
p. bromo benzene sulph. ac. catal. p. toluene sulphonic catal. 
0.00089 mol. 0.00178 mol. 0.00089 mol. 0.00178 mol. 
ko -- 0.0006 _ 0.0003 
k20 0.0032 0.0127 0.0035 0.0064 
k30 0.0119 0.0399 0.0111 0.0216 
K 40 0.0389 0.122 0.0349. 0.0610 
Ks O 155 0.345 0.0846 0.156 


The energy increment calculated from the 1%* series of observations 
without catalyst, and from these 24, 3'¢, 4th, and 5th series is 
respectively + 10.000 calories — 23000 eal. — 20500 cal. — 20500 
cal. — 20800 cal. 

The acetylation of diphenylamin decides, therefore, in favour of 
Scuerrer’s theory, as it would e.g. be entirely inexplicable according 
to Lewis, why the sulphonic acid can act as catalyst, as the addition 
of this substance about doubles the energy-increment; the number 
of active molecules. would, accordingly, be much smaller, hence also 
the number of effective collisions. 

In the ealeulation of the factor B from Scuerrur’s formula, it 
appears to be more than doubled by the catalyst. The favourable 
chance of collision has, therefere, been enlarged, notwithstanding 
the number of active molecules has become smaller. Hence if the 
conversion is to be increased, this smallér number of active mole- 
cules must collide more favourably. Accordingly every collision 
between molecules that are sufficiently rich in energy does not 
always eventuate in conversion, itis probably only a small percentage 
of them that enters into reaction. 

One can form the following conception of this. 

It is not immaterial what part of the acetic acid anhydride 
molecule impinges with the diphenylamin-molecule, nor with what 
part of the latter. The reactive molecule parts, in this case the 


207 


Ist series. 2nd series. 3rd series. 
E B E B E B 
Kop : Kp | 9600 | 12.3 kg : Kag | 23200 | 34.7 k39 : Koy | 20200 | 31.1 
k39 : Ko | 9800 | 12.7 k49 : K3g | 23000 | 34.4 Kyo : K39 | 20800 | 32.0 
Kyo : ko 9800 | 12.6 ks : Kyo | 22600 | 33.8 kso : kyo | 20800 | 32.1 
ks9 : Ko | 10200 | 13.4 


4th series. 5th series. 
| E | B E | B 
k3q : Koo | 20400 | 30.1 kz : Koo | 21600 | 32.7 
K4o : Kgp | -21000 | 31.1 Kyo. : Kao | 20800 | 31.3 
Ks : Kyo | 20200 | 29.8 ks) : Kg) | 20200 | 30.4 


oxygen bridge of the anhydride and the aminohydrogen of the amin, 
must be in each other’s immediate neighbourhood. In a substance 
which exercises an attraction on these two parts, these molecule 
parts will be turned towards each other at a collision of the three 
molecules (more probable is a collision of a molecule with the 
complex of the two others). The sulphonic acids used certainly 
exert an attraction on the amino hydrogen, and most likely also on 
the bridge oxygen, because sulphuric acid impinges with the anhy- 
dride at that place, and the sulphon group is the active component 
in both substances. In my opinion the catalytic action of sulphonic 
acid is for the greater part due to its directive action, and it owes 
this directive action to its affinity towards the reaction components, 
as Borsexen’s dislocation theory demands for every catalyst, without 
this affinity leading to such a firm bond, that the affinity, hence also 
the directive action on the other kind of molecule, would be 
eliminated. 

Against these conclusions the question might be raised whether 
the measured temperature coefficient represents indeed the real one. 
The nature of the catalyst leads to the supposition that a part of the 
sulphonic acid is bound to the diphenylamin resp. anhydride (or 
both), and that this might not be active (or much less so). On rise 
of temperature a stronger dissociation would appear in the components, 
hence more free (i.e. more active) catalyst would be present. Then 


208 


kr+10 ait __ kr+10 Coat T+10 
4 CT Ccat T ’ 


ky ky 


Accordingly the real temp. coef. would be smaller than the 


the measured temp. coeff. is not = 


measured one. 

Let us suppose the bound catalyst to be totally inactive, and the 
true temp. coef. to have remained of the same value as was 
found in the non-catalysed reaction. The measured temp. coéf. 

/ =? 
2 “from which piace 
C cat € cat 
confronted by the question whether it is possible that in the neigh- 
bourhood of room temperature the concentration of the components 
increases by 67°/, per 10° increase of temperature. 

Let us take 300° and 310° absolute for the two temperatures, 
0.1111 as constant of equilibrium at 300° (hence 90°/, bound cat, 
10 °/, free eat), and let us put the heat of dissociation = 5000 eal, 


a heat which may be called-normal. 


= se = 1,67, in other words one is 


f 10 X c4 = axe, 
Asoo 90 EOS 
in which ca =c’,4 may be put: 
Leip RO 
K,,, 100—«# 


It follows from the reaction-isochore that: 


log oii, Oa See _ ee 
7K. 4arl ToT, Berl Osun 
from whieh: 
Baro 1,31 = NW seife 
Keen 100—z 
from which: 
c' cat 
#=12,7 and = 11 
c¢ cat 


Hence even in the most unfavourable case conceivable that the 
bound catalyst would be totally inactive, the increasing dissociation 
per 10° inerease of temperature is only able to account for a small 
part of the inerease of the temp. coef. of the catalysed reaction 
above that of the non-catalysed reaction. 

SCHEFFER pointed out that in many cases the H may be put 
practically constant over a limited range of temperature, and that 
in this case B is also pretty well constant. If the region from 
20°—50° lies within this limited range, the values of mk drawn 


209 


1 =. 
as function of — must lie on a straight line, for every equation of 


the form y—=ma-+6 represents a straight line. Expressed in a 
graphical representation this appears really to be the case‘), and 
the course of the lines suggests that the energy-increment is little, 
if at all, dependent on the quantity of added catalyst. The values 
of Ink at O° fall outside the straight line in the catalysed reactions. 

As on account of the slight velocity of the reaction at O° the 
observations need not be very accurate, | repeated two measurements 
at O°, viz. of the non-catalysed reaction, and of that with 0,00178 
mol. p. bromobenzene sulphonic acid. I extended the observations 
over fully two days instead of over seven hours. 


temp. 0° 1 mol. diph. 12!/, mol. anh. 


temp. 0° 1 mol. diph. 12'/2 mol. anh. 0.00178 mol. acid. 
K : K 
| t 0/) converted 9.303 t Vo converted 2303 
21.55 uur! ~ 8.0 0.00165 21 48 uur 10.3 0.00216 
28.26 >» 10.1 0.00162 28.19 » 12.9 0.00212 
44.55 >» 14.5 0.00152 44.48 » 19.4 0.00210 
52.52 >» 17.6 0.00159 52.44 » 23.8 0.00224 
15.46 > 32.3 0.00226 


Though the values which I found, were indeed lower, the constant 
of the purely catalysed reaction appeared tq have the same value 
as was determined in former experiments, viz. 0,00218—0,00160 = 
= 0,00058 (found formerly = 0,0006). 
0,0127 
(3,1)? 
the gross catalysed reaction 0,00132 + 0,00160 = + 0,0029; a 
value that exceeds the error of observation many times. 

In FeCl, I think I have found a catalyst which is catalytically 
active undiminished down to O°. As these experiments have not yet 
been completed, they will be discussed in a later publication ; | may 
conclude from the experiments already made that also ferri-chloride 
enlarges the “hill” of energy and that accordingly also this catalytic 
action can alone be explained by the aid of Scuurrer’s theory. 


To be expected was a value + = + 0,00132, hence for 


1) Diss. Delft 1922. 


Chemistry. — “The Dislocation Theory of Catalysis.” By Prof. J. 
BORSEKEN. 


(Communicated at the meeting of May 27, 1922). 


The explanation of the catalytic phenomena has always presented 
great difficulties, and has never been satisfactory as yet, because 
the cause of changes of reaction-velocity was to be ascertained with- 
out there seeming to be a clear relation between the velocity of 
reaction and the quantity of energy that came into play. 

Before the catalytic phenomena had been bronght in connection 
with the conception of free energy, satisfaction might be found in 
establishing the fact that one ov more intermediate reactions took 
place, which together proceeded more rapidly than the reaction 
without catalyst. 

And it is still possible to be satisfied with such an explanation 
when it can also be shown that the catalyst in quantity and quality 
is eventually regained unchanged from the reaction mass. 

It should, however, be fully realized that no answer is given to 
the question why these intermediate reactions proceed more rapidly 
than the principal reaction. 

This is the more striking, because in these intermediate reactions 
the catalyst disappears from the reaction-mass at least temporarily 
and partially. I have, therefore, pointed out that the ideal catalysts 
are exactly those that are not fixed in intermediate reactions, and 
that the real catalysis is the interaction between the catalyst and 
the molecules, which has nothing to do with the formation of a 
compound as such. 

This interaction, which I have called dislocation, may be seen as 
a change of the paths of the electrons; it is very well possible that 
it cannot take place until the catalyst has formed @ compound with 
the molecules, but at any rate it must be possible to show it in 
some way or other and to express it in a mathematical form. 

On one side it is therefore necessary to form a clear conception 
of the dislocation, on the other side the modifications which take 
place in the thermodynamic relations through the presence of a 
catalyst and to which the changes of the reaction velocities respond, 
must be fixed in a mathematical formula by establishing a connec- 


211 


tion between the reaction velocities and the thermodynamic relations. 

As regards the former, 7m the owidation of alcohols with coopera- 
tion of aromatic ketones activated by light | have found a reaction, 
in which the catalysis proper (the dislocation) could be sharply 
distinguished from the formation of a coumpound between catalyst 
and the molecules present. *) 

When an alcoholic solution of benzophenon, which is kept 
saturate with oxygen, is exposed to violet light, the alcohol is oxi- 
dized to aldehyde and water, the ketone remaining unchanged. 

A closer study brought to light that above a certain concentration 
of the ketone the velocity of reaction became independent of this 
concentration, and further that it was proportional to the sgware of 
the intensity of the light and to the first power of the conc. of the 
alcohol. 

This may be explained as follows: 

The ketone absorbs part of the light and is activated by it. 
According to the laws of absorption the quantity of active ketone 
will be proportional to: 

T(i—e—*?) in which & = absorption coefficient 
c = concentration ketone 
d = thickness of layer 


Teed is the light that is transmitted. If 4, c, and d are pretty 
great, this is very little, and all the light is absorbed. The quantity 
of activated ketone then becomes proportional to / and independent 
of c, its concentration. 

When we assume that among others the two following processes 
take place: 


2 active ketone + alcohol — (active ketone), alcohol 
and 
(active ketone), alcohol + O = ketone + aldehyde + H,O, 

the former of which proceeds much more slowly than the latter, 
the oxygen absorption (which was measured) will be determined by 
the first process, the velocity of formation of the ternary compound. 
This velocity of reaction must then be proportional to the square 
of / and to the concentration of the aleohol. 

I will not enter here into a fuller discussion how this might be 
proved in different other ways’). The whole process can now be 
described as follows: 

Under the influence of the light there is suddenly formed a 


1) Recueil 40, 433—445. 
2) lc, p. 4839—442. 


212 


quantity of photo-ketone = &:/ (1—e-'«¢) approaching to &/. 

I. ketone + light = photo-ketone ; 
as this quantity is formed at the moment that the solution is illumi- 
nated, it is as if with the velocity of light a plate of a catalyst 
slides on the light side of some vessel or other, in which the solu- 
tion is put. 

Then the reaction takes place the velocity of which regulates the 
process: the meeting of the alcohol molecules and those of the 
photo-ketone : 

II]. 2 photo-ketone + alcohol = (photo-ketone), aleohol. 

By this meeting two H-atoms of the alcohol are activated : 

Ill. (photo-ketone), aleohol — [(photo-ketone), active alcohol]. 

This process, .which probably takes place with the velocity of 
light, zs the real catalysis, the dislocation. 

The aleohol-molecules are enabled to react with the oxygen accord- 
ing to the scheme: 

IV. 2 [(photo-ketone) active alcohol] + O, = 

4 ketone + 2 aldehyde + 2H,O, 
which last process also takes place wilh great velocity. 

We see that the actual catalysis has to do with the formation of 
the ternary compound only in so far as the photo-activity of the 
C= O-groups of the ketone can be transferred to the H-atoms of - 
the alcohol. Here the distinction of the catalysis and of the forma- 
tion of the compound is, indeed, very clear, for the ternary compound 
is also formed in the dark, and then there is no question of any 
catalytic action. 


When the photo-ketone is thought replaced by an ordinary cata- 
lyst, e.g. a plate of paladium, it is clear that the combining of this 
metal with the alcohol is not the essential part of the catalysis, but 
what happens with the alcohol molecules at the moment that the 
atoms Pd get into contact with them, through which two of the 
H-atoms are activated. This the paladium can do by itself, without 
being activated by a stimulus from outside. 

It appeared from the light-investigation that the. oxidation of the 
activated alcohol molecules took place very rapidly. This will as a 
rule also be the case in the ordinary catalysis, but this velocity 
can be different for each case. 

If, however, a catalyst in very small quantities is to accelerate 
a given reaction considerably, every contact of its molecules with 
those of the substance that is to be activated, must give rise to a 
dislocation that sets in very rapidly. 


213 


It is clear that this can hardly take place otherwise than on 
intimate contact, and here the significance of the formation of a 
compound between catalyst and the molecules to be activated, even 
though it be one that can very easily be dissociated, comes to the 
fore. In the light investigation it was only the primary and secondary 
alcohols that were easily oxidized, and not the hydrogen itself and 
a number of hydrogen compounds, evidently because the former 
could, the latter could not be attached by the ketone. 

As has been said in the introduction, not only must the conception 
of dislocation be defined more closely, but it must also be tried to 
find a mathematical form for it through the consideration of the 
thermo-dynamic and kinetic relations. 

Of late years many scientists have occupied themselves with studies 
of the reaction velocities, which are also the subject of this investi- 
gation. We may mention the names of Travutz, Marceiin, Lewis, 
Perri, and ScHEFFER *). ; 

It seems to me that Scurrrur’s considerations have the greatest 
value for the knowledge of the significance of the dislocation, because 
there the question is put whether a formula for the phenomena of 
diffusion (drawn up by Kounystamm) is also valid for the description 
of the reaction velocities, and this question is answered in an 
affirmative sense. 

For the chemical phenomena are essentially phenomena of diffusion 
in which particularities will occur only in the partial mutual pene- 
tration of atoms and molecules. In Scuerrer’s theoretical research 
the significance of these particularities, which were represented in 
the form of thermo-dynamic relations of the “intermediate states’, 
was clear. It is self-evident that it is exactly these relations which 
are modified by the catalyst, and that comparison of these relations 
without and with the catalyst, must lead to a standard of the 
dislocation. 

ScHEFFER’s simple equation of the relation between the reaction 
constant, the quantities in question, and the temperature is: 


1B 10); 
nik = — ——— + B. 
i Rr + 
In this 2, — # is a measure for the difference of energy 


between the reacting substances and the intermediate state at the 
reaction’), 4 contains the differences of entropy and constants 
) These Proceedings Vol. XIII, p. 789 and Vol. XV, p. 1109. 
4) It is the energy which a gram-molecule requires above the mean energy al 


the temp. 7 in order to react, and which is sometimes expressed by the name 
of energy-increment. 


214 


which do not depend on the nature of the reacting substances. 

As a difference of entropy is a measure for a greater or less 
probability, and as this probability must refer to the reaction setting 
in more or less easily, both this difference of energy and this pro- 
bability can be calculated by the aid of this formula from two 
observations at different temperatures, and by carrying out this cal- 
culation with and without a catalyst it can be ascertained in what 
way these two relations are modified by the catalyst. 

As appears from the following communication, this calculation 
has been applied by E. van Tuiet to the acetylation of diphenyl- 
amin with aeetie acid anhydride both in presence of p-bromo (methy])- 
phenylsulphonie acid as catalyst and without it, and the remarkable 
result has been obtained that in the presence of a catalyst the 
factor (£,— FE) is about doubled, £6 becoming also considerably 
larger. The conclusion may be drawn from this that in this ease 
by the addition of a catalyst more than double the energy is, indeed, 
required to cause the molecules to react than without it, but that 
this unfavourable factor is far more than compensated by the so 
much greater probability for the setting in of the reaction in the 
presence of the catalyst. 

In his address at the spring meeting of the Ned. Chem. Ver. 
(Duteh Chemical Association) of April 20 1922 Scuerrer expressed 
this as follows: the hill of energy that is to be surmounted becomes, 
indeed, higher, but the road across it, becomes very much broader. 

Though it may be more or less a coincidence that in the case 
examined by van Tui, the hill of energy is so much higher in 
the presence of a catalyst than without if, it is yet the confirmation 
of my view that the formation of a compound between the catalyst 
and the substances to be activated sooner hampers than promotes 
the reaction, and that the catalyst performs its accelerating action 
not by combining with these molecules, but zn spite of this combination. 

The acceleration of the reaction takes place because simultaneously 
with the formation of this compound a change of condition sets in, 
the dislocation, in which the conditions for the occurrence of the 
reaction become so much more favourable. The conception of dislo- 
cation has found a confirmation through Scuurrer’s theoretical investi- 
gation, and a measure in the variation of the quantity B of his 
formula. 

In conclusion it may still be pointed out that the thermo-dynamic- 
kinetic considerations have not brought the question why a catalyst 
creates favourable conditions, nearer to its solution. The possibility 
may be considered of the molecules assuming a certain position, 


215 


which causes the collisions to take place on the reactive parts of 
the molecules (van TareL, see following communication), or it may 
be supposed that the reactive surface is ‘enlarged, etc. etc. It is 
certain that these changes of position or of form must take place 
very rapidly, and the catalyst must be under very favourable con- 
ditions with regard to the molecules that are to be activated, which 
ean hardly be imagined in another way than ensuing from a che- 
mical affinity, which leads to dissociation equilibria that are esta- 
blished very rapidly. 


Delft, May 1922. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Botany. — “The disappearance of the diploid and triploid magni- 
coronate narcissi from the larger cultures and the appearance 
in ther place of tetraploid forms’. By Dr. W. EK. pr Mot. 
(Communicated by Prof. G. van Iverson JR.). 


(Communicated at the meeting of June 24, 1922). 


I. Introduction. 

Simultaneously with my investigations into the causes which lead 
to the immense variety of size and form in the Hyacinthus orventalis 
in Holland, | commenced a similar research with respect to the 
species of narcissi and narecissus-hybrids under cultivation. These 
comparative researches have led to some noteworthy results. One 
conclusion | arrived at was that, as is the case with Hyacinthus 
orientalis, the remarkable size of the bulbs, leaves and flowers which 
characterize the bastards of Narcissus Pseudonarcissus now cultivated, 
correspond mainly with the number of chromosomes of which, 
according to my cytological observations, the somatic nuclei consist. 

This feature which, as far as I have been able to observe, occurs 
in Hyacinthus ortentalis only in the Duteh cultures, is found both 
in England and in the Netherlands in Narcissus Pseudonarcissus, 
and is more pronounced than in the hyacinta. In the latter there 
are probably no tetraploid plants yet, whereas there are several in 
the Narcissus Pseudonareissus. 


II. Some results of the cytological investigation. 

The preparations which | used in my cytological researches were 
made in the same way as those for hyacinths. The thickness of the 
sections is 10 or 154 according to the size of the cells and nuclei. 

AscnersoN and Grarsner (1) give the Magnicoronati as the 1s 
section of the sub-genus /unarcissus. This section is entirely formed 
by the class N. Pseuwdonarcissus, which they divide into 2 sub- 
classes, NV. festalis and N. minor. For convenience sake in describing 
the varieties studied, I shall keep to this classification, except that 
I shall place the sub-division N. minor first. 


1. N. minor. 


The somatic nuclei of NV. minor (the type), N. nanus, N. minimus 
and NV. cyclamineus (which is best classed with the sub-species 


; 
1 


217 


N. minor) consist of 14 cylindrical chromosomes, 10 long ones and 
10 short ones. 


2. N. festalis. 


a. Diploid varieties. 

The somatic nuclei of N. muticus (syn. abscissus), Capax plenus 
(which perhaps ought to be classed under N. minor), Telamonius 
plenus (Double Sion, Wilmer’s great double golden yellow Daffodil), 
large old double yellow trumpet Daffodil) also comprise 14 chromo- 
somes which I cannot distinguish from the former ones. 

b. Heteroploid varieties. 

N. Johnstoni Queen of Spain possesses somatic nuclei with 20 
chromosomes. In Maaimus and Golden Spur these nuclei consist 
of 21 chromosomes, so that judging from the number these varieties 
are triploid. 

The nuclei of Bicolor Victoria and Buttonhole (obtained from 
Bicolor Victoria by budvariation) contain 22 chromosomes. The 
chromosomes-garniture of both forms is the same. 

The varieties King Alfred and van Waveren’s Giant are, to judge 
from the number of chromosomes, tetraploid, for here the somatic 
nuclei consist of 28 chromosomes. 

In all the 14 forms above-mentioned and examined, the chromo- 
somes — both long ones and short ones — correspond in size and 
shape. The diploid nuclei always consist of 10 longer and 4 shorter 
chromosomes. [ cannot yet state the exact number of long and short 
chromosomes of the nuclei of the heteroploid forms. To do this it is 
necessary to examine over 3000 good sections with dividing nuclei; 
I have now examined this number. Probably the longer and shorter 
chromosomes do not differ in length and breadth from each other, 
and as in Hyacinthus orientalis the pairs of long and short chromo- 
somes will not be distinguishable from each other by any characteristic 
constant difference in form, as is described of N. poeticus by 
Stomps (3). 


Ul. Self-pollination in diploid, triploid and tetraploid forms. 

In contrast with Hyacinthus orientalis, in such categories as can 
be distinguished cytologically, self-pollination yields good practical 
results. From the few seeds of the diploid N. minimus, minor, 
eyclamineus (and N. triandrus albus), taken in 1913, 1914 and 1915, 
I have reared plants which are not distinguishable in bulb leaf and 
flower from the parent species. 

In the case of the triploid Golden Spur self-pollination yielded 

14* 


218 


plants which in form and size differed from each other and from 
the parent species. 

By means of self-pollination of the tetraploid Aing Alfred 1 got 
hundreds of seeds in 1914 and 1915. In 1916 [ had about 1400 
small bulbs. This spring 50 flowers came out, which differed greatly 
in form and size from each other and from Avng Alfred. Most of 
them were smaller than the parent species. The tetraploid Van 
Waveren’s Giant can also be self-pollinated successfully. 


IV. Conclusion. 

1. Of the variety Maximus which I examined we are aware that 
it was already known in 1600, from which it may be inferred that 
even three hundred years ago there was triploidia in the magni- 
coronate narcissi. Triploidia must have commenced with the wild 
species or those again run wild, as the above-mentioned variety 
and (olden Spur (first cultivated between 1885 and 1888) were 
probably not obtained in nurseries (see 6). Regarding the wild 
variety of N. Johnstont Queen of Spain, Baker assumes that this is 
a hybrid between NV. Pseudonarcissus and N. triandrus. If this is 
correct — and the bastards cultivated of these two varieties leave 
no room for doubt — this variety of Queen of Spain is in all 
probability a bastard between a heteroploid form of N. Pseudonar- 
cissus and N. triandrus, as my experience shows the latter to be 
diploid and to possess the same chromosome garniture as the diploid 
narcissi already mentioned. 

2. If we keep to the classification of Ascnerson and GRAEBNER we shall 
see that the feature of the heteroploidia was first seen in the genus or 
group of N. Pseudonarcissus festalis major, the diversity which by 
hybridization has principally yielded the large garden forms of the 
present day. 

It is very interesting how the increase in the size of these varie- 
ties now cultivated can be traced. Up till 1885 — the diploid 
varieties were chiefly grown. The culture of the Golden Spur marks 
the beginning of the era of the triploid garden forms. 

Bastards between Maximus, Golden Spur and other valuable 
kinds are grown, with the result that larger specimens have been 
obtained, of which King Alfred (England; tirm of KunpaL1) is the 
finest. From this dates the advent of the tetraploid varieties (1899). 

Just as the climax in point of size of the diploids seems to have 
been reached in V'elamonius plenus, and of the triploids in Golden 
Spur, the culminating point among the tetraploid forms seems to 
have been reached in Van Waveren’s Giant. Nevertheless this 


219 


has been surpassed again by magnicoronate narcissi, the dimensions 
of which are greater in one or two respects (e. g. Karly Giant, 
Apotheose, Ajax Grand Vizier, Imperator and Mammoth ; (see for 
this the “Weekblad voor Bloembollencultuur’, 32nd. Year, 1922, 
Nos. 85, 87, 89, 91 and 93), so that we may suppose that there 
are already hypertetraploid forms. In this connection the significant 
question arises as to whether the number of chromosomes may go 
on increasing indefinitely. Or, in other words: Is there any Jimit, 
and if so, where? 

The same question has been asked by Brumer with regard to the 
increasing size. (‘“Weekblad” n°. 101). In the following table some 
of the measurements are given in millimetres; they are nearly the 
same as those given in the publication of Sypenaam (4), with the 
exception of those for Mammoth, which are mentioned in ‘‘Week- 
ladders mnt os: 


: Tepals Paracorolla 
Name of variety Diameter Sas ae 
length | breadth} length | breadth 
Queen of Spain 82 35 15 28 28 20 
Bicolor Victoria 101 44 35 44 44 22 
King Alfred 107 40 28 44 50 28 
Van Waveren’s Giant 127 50 38 50 50 28 
Mammoth 140 ? ? 55 60 2 


3. It goes without saying that I cannot now sacrifice the plants 
that I have obtained from King Alfred and (rolden Spur for a 
cytological examination. But even without this examination it seems 
to me highly probable, especially when | test these observations by 
those conducted by Winkier with Solanum (5) and those of van 
Overrem with Od5nothera (2), that these conspicuous differences in 
form and size are primarily due to an unequal distribution of the 
chromosomes in the reduction-dividing of which an unequal combi- 
nation of the sex nuclei ts the inevitable result. 


LITERATURE. 


1. Paut AscHerson and Paut GRAEBNER. Synopsis der mitteleuropaischen Flora, 
Bd. 3, Leipzig, Wilhelm Engelmann, 1905—1907. 

2. CASPER VAN OveREEM. Ueber Formen mit abweichender Chromosomenzahl 
bei Oenothera. Beihefte zum Bot. Centralbl., Bd. 38, Abt. I, Heft 2, 1921. 


220 


3. THeo J. Sromps. Gigas-Mutation mit und ohne Verdoppelung der Chromo- 
somenzahl. Zeitschr. f. ind. Abst. u. Vererb. Bd. 21, Heft 2, 1919. 

4, Ropert SypDENHAM. All about Daffodils. Sec. edition, Midland Daffodil Society, 
1911. 

5. Hans Winker. Ueber die Entstehung von genotypischer Verschiedenheit 
innerhalb einer reinen Linie. Deutsche Gesellschaft fiir Vererbungswissenschatt. 
Bericht tiber die Griindung und die erste Jahresversammlung. Leipzig. Borntraeger, 
1921. 

6. D. M. Wisrennorr and R. H. Berruorst. De Narcis. Leyden, Batteljee en 
Terpstra, 1908. 


Plant physiological Laboratory of Prof. Ep. VERSCHAFFELT, 
Hortus Botanicus, at Amsterdam. 


Mathematics. — “Numbers of Circles Touching Plane Curves 
Defined by Representation on Point Space.’ By L. J. Sip Jr. 
(Communicated by Prof. Henprik bE Vrigs), 


(Communicated at the meeting of June 24, 1922). 


The circles of a plane (degenerations included) may be represented 
without exception through a one-one representation on the points 
of a projective space. (R. Mrenmkr, Zeitschrift fiir Mathematik und 
Physik 24 (1879)). We can arrive at it among others in the 
following way: 

Let W be an umbilical point of a quadric VU? and let w be the 
tangent plane at that point, B a plane, parallel tow. A plane section 
of O? with its pole relative to O* is projected out of W on #5 as 
a circle with its centre, and inversely. We consider this pole as 
the image of the circle. 

As a special case we may take for UO? a quadric of revolution of 
which W is a vertex. If moreover 0? is a sphere, we get the repre- 
sentation of Prof. Jan pu Vries (Verhandelingen 29); if W = moves 
to infinity it becomes the representation of Dr. K. W. Warstra 
(Verhandelingen 25). 

Prof. Hx. pe Vrins has studied cyclographically the circles touching 
a curve C in B of the order u, the class », passing «¢ times through 
both the circle points (with ¢ different tangents in finite space which 
cut C at those points in ¢-+ 1 points), touching the line g,, singly in 6 
different points and having further no other singularities than d 
nodes, # cusps, r bi-tangents and « inflexional tangents (Verhande- 
lingen 8). 

We arrive at the same results through the above mentioned 
representation. We shall only consider the principal ones. 


The curve C is projected out of W on QO? as a curve consisting 
of the two generatrices through JW, counted € times, and a curve & 
of the order n = 2u — 2¢ passing (u—2e)-times through JV. 6 pairs 
of tangents at W coincide, because the parabolic branches of C 
give rise to cusps of & in WW. Further & has d nodes, « cusps and 
(u—e) (u—e—1) apparent nodes and no stationary tangents. By 
means of PLicknr’s formulas we find other numbers characteristic of /. 

From the nature of the representation there follows that the points 
of the surface Z of the tangents of / represent the circles cutting 
C at right angles. The tangent planes to O* at the points of & 


222 


envelop a developable surface A the points of which represent the 
circles touching C and the points of the cuspidal curve / of K 
represent the osculation circles of C. There exists a polar relation 
between the points, tangents, and planes of osculation of & and the 
planes of oseulation, tangents, and points of /. Out of the characte- 
ristic numbers of & and L we find accordingly through dualisation 
the characteristic numbers of / and K, for instance: 


Order of 7: met 3u — be — 26 

Order of K: r = 2u + r— 4 —o 

Cusps of 7: 6 = 5u-- 3v + 3: — 8e — 30 

Order of the nodal curve of A: a = 4${(Qu + »— 4e —o)?—13u—» 
—de + 24 + To}. 


Krom this follows among others: 

To a given pencil there belong r tangent circles of C, but to a 
concentric pencil only »— (g— 2e) in finite space (class of the 
evolute). If we have 3 curves €,,C,,C,, the surfaces K,,K,,,, have 
in all rr, points in common, of which however there lie 
4(u, — 2e,) (u, — 2e,)(u, —22,) in W. The rest is the number of 
circles touching the 3 curves. 

Through a given point there pass m osculating circles of C. The 
projection of / out of W on B&B is the evolute; 7 passes o times 
through W, hence the order of the evolute is m—o. The evolute 
has cusps (vertices of C) in finite space and moreover ~—2e—2o 
at infinity, arising because ~ — 2e — 2o tangents of / pass through 
W, lie in w and have their points of contact outside W. 

Through a point there pass « cireles touching C twice. The locus 
of the centres of these bi-tangent circles is the projection of the 
nodal curve of K. This curve however passes s = (jt— 2¢) (a —2e—1)—o 
times through W, so that the order of the projection is only #—s. 

The number of tangents to / cutting / once more, is y= rm -+ 
t- 12 — 14m —6n. Of these 26(u — 2e — 2) lie in w through W. 
The rest gives the number of circles of curvature touching C once 
more. 


The number of triple points of A’ is: : 
t= 4 fr? — 8r (vr +n + 38m) — 58r + 42n + 78m}. 
Of these however 
(uw — 2e) (« — 2e — 1) (u — Be — 2) 
1 Dye 3 
lie in W. The rest gives the number of circles touching C thrice. 
If we work out these formulas they get the same form as those 


4 


26 (u — 2e — 2) 


of Prof. pe Vains as is to be expected. 


Chemistry. — ‘‘Monochloro-trinitrobenzenes.’ By Prof. A. F. 
HOLLEMAN. 


(Communicated at the meeting of June 24, 1922.) 


So far only two of the six possible isomers were known, viz. 
piecrylehloride and a product obtained by Ninrzxi (see below). For 
an inquiry into the replaceability of substituents if was required to 
prepare also the other four isomers. | have only been able so far 
to lay hands on three, and without doubt I should have waited 
with the publication of my results till the whole investigation had 
been completed, if ] had not happened to hear that also others are 
engaged in a study of the same subject. 


Cl 1-chloro-3, 4, 5-trinitrobenzene. This compound is 

aN easily accessible ; it is indeed surprising that it has 

1G | | not been known long since. The starting-point for 

NO TNO, its preparation is chlorodinitraniline 1, 4, 2,6, in which 

; 2 NO, was substituted for the NH, group according 
to the method of Korner and Conrarpr. The yield Cl 
of raw compound amounts to 70°/, of the theory, VIN 


and there is only little loss in the purification. The 
substance may be recrystallized from benzene. It NO,\Y/NO, 
then melts at 168°. Large yellow crystals. 2 
Cl 1-chloro-2, 3, 5-trinitrobenzene. This compound is 
oe formed on very energetic nitration of 1-chloro-2,3- 
* dinitrobenzene with a mixture of fuming nitric acid 
NO,\/NO, and oleum of 50°/,. The heating of 160—170° is 
continued for 5 hours. When the mixture is poured out into water, an 
oil is obtained, in which crystals are formed after some time. By centrifu- 


HL. 


gation these are separated and then recrystallized from alcohol. Melting- 
point 106°. The structure of this compound was verified by a treatment 
with alcoholic ammonia, through which 2-chloro-4,6- Cl 
dinitraniline is obtained, melting-point 159°. This com- Pn 
pound is known. Much more easily, however, than - 
according to the methods used up to now it could be NO,\/NO, 


prepared by chlorination of NH, 2-4-dinitraniline with KCIO, 
in hydrochloric acid solution. —§ 7\ NO The entrance of a NO,-group 
at the place 5 in 1-mono- | * chloro-2,3-dinitrobenzene is 
very surprising, as this WA group takes a position at am 


with regard to Cl and at p with regard to a nitro-group. 


224 


Cl 1-chloro-2,3,4-trinitrobenzene. In the nitration of 
c 1-chloro-2,3-dinitrobenzene by the method given 

“NNO, me 5 2 
AH ee) | under UU, the oil from which II was crystallized 


\ZNO, contains this third isomer. When the oil stands for 
NO, a long time, the isomer crystallizes out of it in 
colourless needles of the melting-point of 69°. They are purified by 
recrystallization from alcohol. The structure of this compound can 
also be determined by treatment with alcoholic ammonia. If the 
action of the ammonia is allowed to last only for a short time, 


only one of the nitro-groups is replaced by NH,. Cl 
The aniline formed is 3-chloro-2, 6-dinitraniline for ce NO, 
l-chloro-2, 4-dinitrobenzene is obtained from it | 
by deamidation. This aniline has the melting-point yal 
112°; it was unknown up to now. 
Cl 1-chloro-3, 4, 6-tr nrabeiaene This compound was 

NOS already prepared by Nrierzki by nitration of 1-chloro- 

HY, =| 3,4-dinitrobenzene. On repetition of his experiments 


\/NO. it appeared to me that the yield was small, and 

NO, especially very uncertain, because either the nitration 
remains incomplete, or the reaction is so violent that total destruction 
ensues. It is therefore, better to proceed as follows : 


Cl NH, NO, 
NOWaN NOWAN NODS 
leietabiN toe | | 

\/a \AEl Wel 
NO, NO, NO, 


The substitution of NH, for Cl takes place in alcoholic solution 
on the waterbath with addition of gaseous ammonia, till a test- 
sample shows the correct melting-point of 174°. According to KOrNnEr 
and Contarpt NO, can then be substituted for NH,. The crude 
product is coloured black. It can be purified by boiling with nitric 
acid 1.4, followed by recrystallisation from alcohol. The melting- 
point is 116°, as has been given by Niprzx1. 


No method of preparation Cl has as yet been found for the 
last isomer, the 1-chloro-2,3, NO ihiipe 6-trinitro-benzene ; probably 
it is also present in the oil obtained in the nitration of 


1-chloro-2,3-dinitrobenzene. \ 120, 
Amsterdam, June 1922. Org. Chem. Lab. of the University. 


Physiology. — “On Respiratory Oscillations in the Galvanogram 
of Man.” By A. A. Weixperc. (Communicated by Prof. 
KE. D. Wiersma.) 


(Communicated at the meeting of June 24, 1922). 


An inquiry into the psycho-physiological significance of the psycho- 
galvanic reflex, which will ere long be reported in detail, gave rise 
to the question whether the respiratory arhythmiae in the plethysmo- 
gram which result from a predominating influence of the sympathetic 
nerve, or of the vagus, on the heart'), may be attended with 
oscillations in the so-called rest-current of the galvanogram. In order 
to set this question at rest the following experimental arrangement 
was set up. 


Our subjects were healthy individuals from 20 to 40 years of age, without any 
anomalies of the heart or the urine. The current was lead off by non- polarizable 
electrodes from the baths of a four-cell bath, and was-registered with the quick 
sensitive electrocardiograph of Sremens and Haske. The non-polarizable electrodes 
consisted of porous pots filled with a saturated zinc-sulphate solution, with a zinc 
rod. These pots were placed in the baths, which contained a physiological NaCl- 
solution heated to body-temperature. The current was recorded by the compensation- 
method, as the condensator-method') does not enable us to observe the slow 
oscillations of the current. The sensitivity of the galvanometer, which was controlled 
for each separate registration, amounted to 4 m.V. per cm. For convenience’ sake 
I selected the three leads which are generally used for taking an electrocardiogram. 
The method of EtnrHoven and Roos’), which implies the use of fingerelectrodes 
and has the advantage of not being complicated by the electrocardiogram, did not 
yield satisfactory results in these experiments. For further particulars of the pro- 
cedure of the experiments I refer the reader to my article in the “Nederlandsche 
Tijdschrift voor Geneeskunde’’ (I.c.). 


With all the subjects thus far examined in this way (fifteen) 
respiratory oscillations were noticeable in the level of the electric 
curve. The only requisite was that the subjects had to be in a 
condition of perfect quiescence, and that their attention be not 
diverted by anything. Directly when they were more or less pre- 


1) A. A. Wernsere, Ned. Tijdschrift v. Geneeskunde; 66, II, 343, 1922. 
*) W. Eintuoven and J. Roos, Pfliiger’s Archiv; 189, 126, 1921. 


226 


occupied, either in consequence of the experiment or through the 
after-effect of emotional occurrences, the respiratory oscillations dis- 
appeared from the galvanogram, while in the case of still intenser 
preoccupation other modifications in the level of the curve appeared, 
which were independent of respiration. All these modifications in 
the shape of the galvanic curve run parallel with the oscillations in 
the level of the plethysmogram, either in the same or in the opposite 
direction. Curve I is an illustration of the respiratory oscillations 
in the galvanogram. 

The following objections may be raised to the hypothesis that- 
these oscillations are connected with the respiratory oscillations in 
the equilibrium between the sympathetic and the parasympathetic 
(vagus resp.) nervous system : 

a. The oscillations are effected by the movements of the respir- 
ation-muscles. 

6. They are caused by the changes in the electrical resistance 
which are brought about by rhythmic movements of the arm during 
respiration. 

c. They are caused by the respiratory oscillations in the blood- 
filling of the extremities. 

The first objection is done away with by the fact that in the case 
of preoccupation the fluctuations disappear (curve II} whereas the 
movements of the respiration-muscles continue. This phenomenon 
might likewise tell against the second objection, just as the fact 
that the subject always rested his hand on the bottom of the arm- 
baths, Hereby the movements of the upper-arm, which were already 
none too vigorous at first, were considerably relaxed if not checked 
entirely. However, with six subjects I have registered the movements 
of the upper-arm with the aid of a very sensitive tambour affixed 
to the arm-bath, its rubber membrane, which is provided with a 
knob, resting on the m. biceps. Hereby it was proved that the move- 
ments of the upper-arm do not affect the shape of the galvano- 
oram. This is illustrated in Curve Ill where the movements of the 
upper-arm are reproduced graphically ; of oseillations in the level 
of the galvanic curve, on the other hand, no trace is to be seen. 
Curve 1V further shows that even considerably stronger involuntary 
arm-movements do not alter the shape of the galvanogram. 

Finally, that the electric modifications in respiration cannot be 
ascribed to the bloodfilling of the extremities is demonstrated by 
curve V, which exhibits distinct respiratory oscillations of the galvano- 
gram, although the extremities, from which current were derived, 
had been made bloodless by bandaging. 


Plethysmagram 


Insp 


Respiration 
: Exp 


Galyanogram 


Time ('/; sec.) 


“IL. The same. 3 VI ’22 Lead I. Comp. 
Pre-occupation curve. 


Movement- 
curve; left 
upper-arm 


IV. G.T. 2 39 years 6 VI’ 22. 
Lead III. Comp. Rest-curve, 


with control. 


a I. G. T. H. @ 22 years 3 VI ’22. Lead I. Comp. Rest-curve. 


Movement-curve ; 
right upper-arm. 


Il. S.v.d.G. 2 31 years 19 VI’22. 
Lead II. Comp. Pre-occupation- 
curve, with control. 


ae Le a 


SRN 
<i (gina 4 yi 


V. D.T. o& 21 years 9 VI ’22. Lead II. Comp. 
Rest-curve with dehematized right arm and 
left leg. Plethysmogram left hand. 


228 
SUMMARY. 


The galvanogram of Man displays with a low degree of conscious- 
ness, oscillations which run parallel to respiration and are very likely 
connected with the respiratory oscillations in the condition of balance 
in the involuntary nervous system, as these oscillations disappear 
with preoccupation and as they are not influenced by the involuntary 
respiratory movements of the arms and are not the outcome of the 
modifications in the bloodfilling of the extremities, from which the 
current is derived. 

From the Laboratory for Psychiatry 

June 1922. of the Groningen University. 


KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN 
TE AMSTERDAM. 


PiwoOGCeE DINGS 


VOLUME XXV 
Nes, 7 and 8. 


President: Prof. F. A. F. C. WENT. 
Secretary: Prof. L. BOLk. 


(Transiated from: "Verslag van de gewone vergaderingen der Wis— en 


Natuurkundige Afdeeling,” Vol. XXXII). 


CONTENTS. 


EuG. DUBOIS: “Phylogenetic and Ontogenetic increase of the Volume of the Brain in Vertebrata”, 
p. 230. 

R. MAGNUS and A. DE KLEYN: “A further Contribution concerning the function of the Otolithic 
Apparatus”, p. 256. 

L. RUTTEN: “Cuba, The Antilles and the Southern Moluccas”, p. 263. (with one plate). 

B. SJOLLEMA and J. E. VAN DER ZANDE: “Changes in Milk due to Sterile Inflammation of the 
Udder”. (Communicated by Prof. C. EYKMAN), p. 275. 

M. W. BEIJERINCK and L. E. DEN DOOREN DE JONG: “On Bacillus polymyxa”, p. 279. 

W. VAN DER WOUDE: “On the Light Path in the General Theory of Relativity”. (Communicated by 
Prof. H. A. LORENTZ), p. 288. 

G. BREIT: “Calculations of the effective permeability and dielectric constant of a powder’. (Com- 
municated by Prof. H. KAMERLINGH ONNES), p. 293. 

J. J. VAN LAAR: “On the Heat of Mixing of Normal and Associating Liquids”. (Communicated by 
Prof. H. A. LORENTZ), p. 309. 

J. BOEKE: “On the Regeneration of Sensitive End-corpuscles after section of the nerve”, p. 319. 

H. R. KRUYT and C. F. VAN DUIN: “Heterogeneous catalysis and the orientation of adsorbed 
molecules”, p. 324. 

H. A. BROUWER: “Fractures and Faults near the Surface of Moving Geanticlines. II. Abnormal 
Strikes near the Bending-points of the horizontal projection of the Geanticlinal axis”, p. 327. 

P. VAN ROMBURGH and J. H. N. VAN DER BuRG: “Cyclic Derivatives of Mannitol”, p. 335. 

F. A. H. SCHREINEMAKERS: “In-, mono- and divariant equilibria’. XXII, p. 341. 

B. L. VAN DER WAERDEN: “Ueber Determinanten aus Formenkoeffizienten’. (Communicated by 
Prof. L. E. J. BROUWER), p. 354. 

H. J. BACKER: “The dissociation constants of sulphonacetic and «-sulphonpropionic acids”. (Com- 
municated by Prof. P. VAN ROMBURGH), p. 359. 

ARIE QUERIDO: “On the progress of the veratrin-poisoning of the striated frog-muscle”. (Commu- 
nicated by Prof. G. VAN RIJNBERK), p. 364. 

L. BOLK: “The Problem of Orthognathism”, p. 371. 

Erratum, p. 381. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Palaeontology and Zodlogy. — ‘Phylogenetic and Ontogenetic 
Increase of the Volume of the Brain m Vertebrata”. By 
Prof. Eve. Dvusois. 


(Communicated at the meeting of June 24, 1922). 


One of the most striking and important palaeontological facts ever 
brought to light in the investigation of the strata of the earth, is 
that of the extremely slight volume which the encephalon possesses 
in the earliest forms of Reptiles, Birds and Mammals. By this 
feature do these for the rest very differentiated and often gigantic 
earliest representatives of their class differ from the forms immediately 
following them and from the modern ones, in a way which must 
almost seem ridiculous to the comparative anatomist. 

As regards Reptiles this has especially become known, by the 
discoveries of Marsu, about the Dinosauria, the principal terrestrial 
animals of the Mesozoic Era. In them the spinal canal, in its whole 
length, was not seldom wider than the cranial cavity. In Stegosau- 
rus, from the Lowest Cretaceous in Wyoming, the cross-section of 
the sacral enlargement of the spinal canal (this in connection with 
the large hind-legs) was ten times as large as the cranial cavity. In 
a Diplodocus of a computed body length of 24 meters, from the same 
strata, this cavity is only 9 cm. long and 5 em. wide, whereas that 
of an adult alligator, with a tenth of that maximum body length of 
its mesozoic distant relation, has a length of 6'/, cm. and a width 
of 3 cm. Also in Theromorpha and Pterosauria the cranial cavity 
is very small. 

Ichthyornis, described by Marsa from the Upper Cretaceous of 
Kansas, possessed only the third of the cranial capacity of the Large 
Sea Swallow (Sterna cantiaca), with which this toothed Mesozoic bird 
bore considerable resemblance in size and structure of its skeleton, 
probably also the mode of life of the two birds was similar. 

In the class of the Mammalia, the Eocene primitive Carnivora, the 
Creodontia, possessed very little encephalon, which appears clearly 
on comparison of the cast of the brain-cavity of Aretocyon, from 
the Basal Kocene of Reims, with that of a dog of similar size of 
body (Fig. 1, A). The Condylarthra from the Lower Eocene, from 
which the existing sub-orders, the Perissodactyla and Artiodactyla 


231 


both originated, had also brains of incomparably small volume; side 
by side with the brain cast of Phenacodus, from the Wasatch 
Formation of Wyoming, that of a pig of similar size of the body 
appears as gigantic (Fig. 1, B). Also other Kocene Hoofed Mammalia, 
the Amblypoda, had very small brains. Thus Coryphodon, from the 
Wasatch Formation, in comparison with a Rhinocerds of similar 
size (Fig. 1, C). 


<<} . 


Fig. 1. Brain cast of: A. Arctocyon and Canis; B. Phenacodus 
and Sus; ©. Coryphodon and Rhinoceros. (After Osponn) !). 


In all these cases the most compounded, functionally most intri- 
cate parts of the encephalon, especially the cerebrum (hatched in 
Fig. 1), have the smallest volume. They in particular have not yet 
come to a fuller growth. But in the Miocene, partly already in the 
Eocene Period, the brain in the Mammalia reaches the volume and 
the proportion of its sub-divisions of most modern types. 

As remarkable as this sudden, at all events comparatively rapid 
increase of the volume of the brain in the classes of Reptiles, Birds, 
and Mammals is the other paleontological fact, that in the Hominides, 
which geologically do not appear until very late, the brain imme- 
diately possessed the same volume already in the earliest of the 
known crania as in modern ones. The expectation that by means of 
these skulls a gradual increase of the volume of the brain might 
be shown, up to the exceptional capacity whose possession raises 


1) H. F. Ossorn, The Age of Mammals in Europe, Asia and North America, 


p- i73. New York 1910. 
15* 


232 


modern Man so high above the animals, has not been realized. 
This however does not apply to Pitheeanthropus, if this fossil 
anthropomorphous Primate is not considered to be of a separate 
family, but reckoned to belong to the Hominides. For he possessed 
only two thirds of the cerebral volume of the Australian aboriginal 
(which he resembled in body size and also in the main features of 
his skeleton), but tvice that of anthropoid apes of the same body 
size. But also this ‘‘preeursor of Man” is of a late date — probably 
not before the Pliocene. The transition from such a volume of brain 
as that of the Anthropoid Apes to the modern human volume seems 
at all events to have been a rapid one, and halfway there is still 
that of Pithecanthropus. 

This organ, upon which depend inscrutable attributes of animal 
life, of the greatest degree, shows therefore. an indubitable progress 
in the geological past. But it is also certain that this phylogenetic 
growth of the encephalon, as a whole and in its most compounded 
parts, took place with starts, and much seldomer than that of the 
other parts of the body, of which now one part, now another is 
again and again seen, in the most diversified ways, to increase in 
volume and complexity, the whole body not seldom growing into 
gigantic dimensions. 

The question now suggests itself what the proportion has become 
between the volume of the brain and the size of the body through 
phylogenetic and ontogenetic growth, i.e. increase from species to 
species and from individual to individual, in adult animals of the 
present time. 

It can easily be ascertained that the brain volume, reached by a 
species of animals in adult state, depends both on the size of the 
body and on the stage of development attained by the brain, which 
determines the degree of the functions of the organ. 

It is not astonishing that the absolute brain weight of Man is 
surpassed by that of the Elephant and the large whale species. 
The largest whale species, which is a thousand times heavier than 
Man, possesses five times his brain weight. It is also self-evident 
that such a gigantic species of the cat family as the Tiger has much 
larger brain than the Domestic Cat; to sixty-four times the body 
weight of the latter, the Tiger has ten times its brain weight. Keeping 
to the same species we find in an adult dog of the size of the 
Wolf, of about 40 kg. body weight, double the brain weight 
of a lap-dog weighing about 2 kg. 

But besides on the size of the body, the brain volume depends 
also on the stage of development of this organ, on the particular 


233 


structure and functions of other organs, and on other not easily 
measurable factors which determine the cephalisation of the 
central nervous system. When we compare Man with animals of 
the same body weight, when, in other words, we eliminate the factor 
body weight, we see that he far surpasses all the animals. He 
possesses three times the brain weight of a species of anthropoid 
apes of the same weight and mere than six times that of an equally 
heavy gazelle. We may also say that the coefficient of cephalisation 
x of Man is three times as great as that of Anthropoid Apes and 
more than six times as great as that of the Gazelle. 

We may assume equal cephalisation for the Cat and the Tiger, 
and yet we see the body weight increase in a much greater pro- 
portion than the brain weight. The same fact is found on comparison 
of the Mouse with the Rat, of the Pigmy Antilope with the Beisa- 
Antilope ete. Evidently the weights of brain and body, also with 
equal development of that organ, are not simply proportional to 
each other. The large species of the same genus, and also the large 
adult individual of the Domestic Dog species always has less brain 
weight in ratio to the body weight than the small species and the 
small adult individual. On account of the equality of the densities, 
the volumes may be substituted for the weights, and itis, therefore, 
possible that another measure of the body than the volume, for 
instance the surface, which is proportional to the ?/; power of the 
volume, — for which the weight P of the large animal may be put, 
and the weight p of the small one, — determines the quantity of brain 
— volume or weight — of the species. A priori it seems, indeed, that 
there is a good deal to be said for this view, for the sensual areas, the 
physiological cross-sections of the muscles, which determine muscular 
foree, the superficial extent of the body, on which metabolism 
depends, are proportional to the surface of the body. The brain 
weights # and e of two animals differing only in body weight, but 
with for the rest quite identical organisation, may always be put 
H=xP and e=<xp"; then the exponent of relation 7, indicating 
the power of the body weight with which the brain weight increases 


log K—I 
or decreases, can be calculated from the equation r= ph amid A 
log P—log p 


Bratests 
and x = Pp will be found. 
Twenty-five years ago, making use of the observations of weight 
published by Max Weper') a year before, I found thus 5/5 as mean 
1) Max Wenser, Vorstudien tiber das Hirngewicht der Saugethiere, in Festschrift 
fiir Cart GecenBaur, p. 105—123. Leipzig 1896. 


234 


value of 7 in seven pair of mammalian species, i.e. a slightly smaller 
exponent than would correspond to the proportionality of the brain 
weight with the surface dimensions of the body '). The discrepaney 
appeared to be constant, and the same exponent was found for 
Birds by Lous Lapricque and Pinrre Girard in 1905*), and for 
Reptiles and Fishes by me in 1913%*). The exponent 5/9 holds un- 
doubtedly for all Vertebrata. Certainly this “strange power” of the 
body weight cannot be attributed to insufficiency of the data; it is 
impossible that we have to do here with a ‘‘rough empirical law, 
as limit of a sum of different functions”. The relation found between 
the weights of the brain and the body must be a simple, rational 
one. As this exponent indicates the relation of species to species, a 
relation which must have come about with the origination of the species, 
I will designate it here as phylogenetic exponent. 

In the system of codrdinates of Fig. 2 the body weights in kg. 


200 


150. 


100. 


1) Eve. Dusors, De verhouding van het gewicht der hersenen tot de grootte van 
het lichaam bij de Zoogdieren. Verhandelingen der Kon. Akademie van Weten- 
schappen te Amsterdam. Tweede Sectie. Deel V, N°. 10. 1897. — Also: Sur le 
rapport du poids de l’encéphale avec la grandeur du corps chez les Mammiferes, 
in Bulletins de la Société d’Anthropologie de Paris 1897, p. 337—376. 

2) Comptes Rendus des séances de l’Academie des Sciences. Paris 1905, 1, 
Tome 140, p. 1057—1059. 

3) These Proceedings, Vol XVI, p. 651—654. 1914. 


235 


are indicated on the abscissa, the brain weights in gr. on the 
ordinate. The points Z, V, F, and L refer to the averages of those 
weights of the species Canis zerda, Canis vulpes, Canis familiaris 
and Canis lupus. The relation of brain weight and body weight in 
these species of the genus Canis is here graphically represented by 
the full exponential curve Z V L, defined by the equation # = 0.41 
Ps, and by the point F, whose position is defined by the 
equation 89 = 0.385 « 18000%. In Fig. 3 the same relation is 


fog 1000 3.0 é 
c 0 
8 

Pil “E IRs 
7 C.lupus 40000 1476 
i C.famil. 18000 89 


C.vulpes c120 s2 
C.zerda 2000 279 


tog. 100/2. 


pete t 


; : By 


c).zet ee =F 


b 


3 
2 


fog, 10! 1.0 
Gromer ame stl an's acm ns wrolZ OME em Ss 45.6.7) 8. 9 50 


fog 1000 ' log 10000 fog. 160000 
Fig. 3 


represented by the full logarithmic line, a straight line with which 
the lines of genera and species with other cephalisation would run 
parallel. 

An entirely different exponent of relation, viz. about 1/;, i.e. less 
than 5/13, half the value of the exponent holding from species to 
species, was found on comparison of large adult individuals of one 
and the same species by Lapicque for the Domestic Dog ') in 1898, 


1) L. Lapicgue, Sur la relation du poids de l’encéphale au poids du corps. 
Comptes rendus de la Société de Biologie. Paris 1898, p. 63. 


236 


and independently of the distinguished French physiologist, in the 
same year, by me for Man‘). In 1907 this result was confitmed by 
Lapicgve’) for Man; at present, from the new observations of weight 
on 150 Berlin dogs by Brrruonp Krarr*) 1 can corroborate the 
result obtained by Laricqur from Ricuer’s 188 Paris dogs *). 

Similar low interindividual exponents-of relation as for Man and 
the Domestic Dog are now also valid within other species. For 
obvious reasons: very important differences of the body weights in 
one case, numerousness of the observations of weight in the other, 
the species Domestic Dog aud Man are most suitable for a comparison 
of the individuals. But we so often meet with similar values, lying 
in the neighbourhood of 5/15 = 0.27 or lower, within other species, 
that here the existence of another, but equally real law may be 
admitted. 

The same relation of brain weight and body weight as between 
large and small adult individuals of Man and the Dog is certainly 
also valid for the Horse. The data are not very numerous here, 
but the differences in body weight are comparatively large. A 
heavy Belgian horse, according to Cornevin*®), weighed 1040 kg. 
when alive, and its cranial capacity was 805 c.c.; a light Camargue 
horse had only 320 kg. living weight, and its cranial capacity 
was determined at 585 ¢.c. From this an exponent of relation of 
0.2708 can be calculated. Prof. J. C. Ewart at Edinburgh was so 
kind as to send me, for measurement, the skull of a very typical 
Shetland pony, a mare of 36'/, inches or 92'/, em. height. Length 
of skull, from ineisivi to occiput, 40'/, em. The capacity is £75 c.c. 
I owe to Dr. C. Kersert the communication of the body weight 
of such a pony living in the Amsterdam zoological gardens, a male 


1) Kua. Dupois, Ueber die Abhingigkeit des Hirngewichtes von der Kérper- 
grosse beim Menschen. Archiv fiir Anthropologie. Band 25, p. 423—441. Braunsch- 
weig. 1808. 

*) L. Lapicgue, Le poids encéphalique en fonction du poids corporel entre 
individus d'une méme espéce. Bulletins et mémoires de la Société d'Anthropologie 
de Paris. Séance du 6 Juin 1907. 5me Série, Tome 8, p. 315. Paris 1908. 

8) Burtnotp Katt, Studien zum Domestikationsproblem: Untersuchungen am 
Hirn. Bibliotheca Genetica (E. Baur). Band II. 180 pag. My calculations are to be 
published in Bijdragen tot de Dierkunde. XXII. Hat sich das Gehirn beim Haus- 
hunde, im Vergleich mit Wildhundarten, vergréssert, oder verkleinert? Leiden 1922. 

4) Guartes Ricuet, Poids du cerveau, de la rate et du foie, chez les Chiens de 
différentes tailles. Physiologie. Travaux du Laboratoire de M. Cuartes RicHEr. 
Tome Deuxiéme, p. 381—397. 

5) Cu. Cornevin, Examen comparé de la capacité cranienne dans les diverses 
races des espéces domestiques. Journal de médecine vétérinaire et de zootechnie, 
publié a |’Ecole de Lyon, 3m Série, Tome 14, p. 24. 1889. 


Ne eee eee 


237 


horse of the same height (92 em.) and skull length (41 em.); it 
was 128 kg. By comparison with Cornrvin’s heavy Belgian horse 
I now find and exponent of relation of 0.2528. The heaviest of 15 
male horses, according to Corin’), a Percheron of 501 kg. dead 
weight, compared with the lightest male horse (‘de petite taille’) of 
this group, of 288 kg. dead weight, gives an exponent of relation 
of 0.1855. The heaviest horse was probably less emaciated than 
the lightest; hence the exceedingly low exponent. 

For two groups, each of six domestic rabbits, formed from 
Miier’s records’), one of an average body weight of 4386 gr., 
the other of 1727 gr., I find an exponent of relation of 0.2512. 
Two groups, each of five male moles, from Manovvrirr'), yield 0.234. 

Eight domestic ducks, of 1756 gr. average body weight, compared 
with a dwarf of the same domestic species, of 755 gr. body weight, 
according to Timann’s*) records, yield an exponent of relation of 
0.3096. A cock of 1745,7 gr. body weight with a hen of 985.2 gr., 
from Fatcx’s ‘) report, yield an exponent of relation of 0.2248. 

Two groups, each of six Bull Frogs (Rana catesbyana), according 
to Donatpson*), of 244.5 and 164 gr. mean body weight, give an 
exponent of relation of 0,2516. Also the average cranial capacities 
of 9 male and 11 female Australian aboriginals in relation to the 
mean volumes of the six long bones, from HavceEr's observations’), 
yield an exponent of 0.2770. 

In the Figures 2 and 3 the dotted lines give a graphical record 
of the relations of the weights of the brain and the body between 


1) G. Coun, Traité de physiologie comparée des animaux. 3™e Edition, Tome I, 
p- 302. Paris 1886. 

8) E. MiitteR, Vergleichende Untersuchungen an Haus- und Wildkaninchen. 
Zoologische Jahrbiicher. (Spengel). Abteilung fiir Allgem. Zoologie and Physiologie 
der Tiere. Band 36, p. 585. Gesamttabelle XXVa. Jena 1919. 

8) L. Manouvrier in Dictionnaire de Physiologie par Cx. Ricuer, article 
»Cerveau”, p. 680. Paris 1898. 

4) O. Timmann, Vergleichende Untersuchungen an Haus- und Wildenten. Zoolo- 
gische Jahrbiicher, ibid., p. 653. 

5) C. Pu. Fauck, Beitrage zur Kenntnis der Bildungs- und Wachsthumsgeschichte 
der ThierkGrper. Schriften der Gesellschaft zur Beférderung der gesammten Natur- 
wissenschaften zu Marburg. Band 8, p. 242. Marburg 1857. 

6) H. H. Donatpson, On a Formula for Determining the Weight of the Central 
Nervous System of the Frog from the Weight and Length of its Entire Body. 
University of Chicago. Decennial Publications. Vol. 10. (1902), p. 7. 

7) Orto Haveer, Der Gehirnreichtum der Australier und anderer Hominiden, 
beurteilt nach ihrem Skelet. Anatomische Hefte (Merxri und Bonney). I. Abteilung. 
Heft 179. Band 59, p. 589: Tabelle I, p. 616—617: Tabelle Ill. Mtinchen und 
Wiesbaden 1921. 


238 


adult individuals of four species of the genus Canis. In Fig. 2 they 
are again exponential curves, defined, for the Domestic Dog, by the 


equation # = f P°*4—8.475 P24 (in which fis found from 

89 = / < 18000), and for the wild Canidae, # = 4.615 Pio(in which 
aie 52 : 

4.615 = In Fig. 3 they are straight lines, both of them 


6120 ‘hs 
less steep than the lines for these relations from species to species, 
which they intersect in the points of the means, as far as the wild 
species are concerned. | have derived the mean point for the Domestic 
Dog, and the line for theindividnal relation within this species from 
observations of weight.on 434 dogs, i.e. 152 new ones by Kiar’), 
Ricuet’s 188 observations *), Lapicque and Dufrk’s 47 *), Ripinerr’s 
19 *), Winper’s 16°), Max Weber’s 12°). On the ground of these 
data 18 kg. may be admitted for the mean weight of the Domestic 
Dog, 89 gr. for its mean brain weight. The brain weight is certainly 
at least 6°/,, probably 10°/, lower than in a wild species of Canis 
of the same weight. This can only be considered as a consequence 
of domestication, i. e. of unnatural mode of living. Something of 
the same kind was found by DonaLpson and Harat’) in the domesti- 
cated albino-form of the Brown Rat (Mus norvegicus). Not only 
the body weight has been reduced in this domestic Rat, but the 
brain weight comparatively to a greater degree, a phenomenon of 
domestication due to a diminished growth of the brain, which was 
already known to Darwin (1868) for the domestie Rabbit *), and 
which was afterwards confirmed by Lapicque’), Kiart**), and 


1) B. Kuart, l.c. Haupttabelle at the end of his work. 

3) Cu. Ricuet, l.c. 

5) L. Lapicque in Bulletins et mémoires de la Société d’Anthropologie de Paris 
1907, p. 316. 

4) N. Riipiva@er, Ueber die Hirne verschiedener Hunderassen. Verhandlungen der 
Anatomischen Gesellschaft. Jena 1894. Erginzungsheft zum 9. Band (1894) des 
Anatomischen Anzeigers, p. 173—176. 

*) B. G. Wiper, Cerebral Variation in Domestic Dogs. Proceedings of the 
American Association for the Advancement of Science, 22"4 Meeting (1873), p. 235— 
236. Salem 1874. : 

6) Max Weber, Vorstudien iiber das Hirngewicht der Sdugethiere l.c., p 112. 

7) H. H. Donatpson and Sxivxisu1 Harat, A Comparison of the Norway Rat 
with the Albino Rat. Journal of Comparative Neurology. Vol. 21 (1911), p. 417— 
458, particularly p. 454—455. 

8) Ca. Darwin, The Variation of Animals and Plants under Domestication. Chap. IV. 

8) L. Lapicque in Bulletins et mémoires de la Société d’Anthropologie de Paris 
1907, p. 331—337: ,Régression cérébrale des animaux domestiques”’. 

10) B. Kiar, Ueber die Veranderung der Schidelkapazitit in der Domestikation. 
Sitzungsberichte der Gesellschaft Naturforschender Freunde zu Berlin. 1912, p. 155 


239 


Miriier'). The same cerebral regression by domestication was found 
by Lapicque’) for the Ox and the Sheep, by Kiarr’) and Berncks *) 
for the Ferret, by Lapicque*) and Timmann *) for the domestic Duck, 
and now by me for the Domestic Dog. For 72 of Donatpson and 
Hatai’s wild Mus norvegicus‘) of both sexes, of 335 to 525 gr., 
averagely 389.861 gr. body weight, with averagely 2.402 gr. brain 
weight, and 71 male and female wild rats of 275 to 325 er., 
averagely 300.211 gr. body weight, with an average brain weight 
of 2.299 er. I calculate an exponent of relation of 0.1674. That 
this exponent is considerably smaller than is usually found between 
individuals of one species, may be readily explained in this way 
that DonaLpson and Hara give the body weights irrespective of 
the state of adolescence and the fat percentage (of which they state 
that it augments with age); part of the increase of the body weight 
is, therefore, not accompanied by increase of the brain weight, as 
is the case on comparison of adult individuals only, and which are 
in a medium condition. 

In Fig. 4, after Donatpson’) the exponent of the individuals with 
body weights between 250 and 446 gr. may be calculated at 0.1572 
for the male wild Mus norvegicus (from observations of weights on 
232 male specimens of all ages). From Donatpson’s Table 85 °) 
the exponent 0.1554 may be calculated for body weight of 301.0 
to 389.7 gr. The exponent is 0.1342 for the male albino of this 
species of 181 to 350 gr. body weight. The relatively smaller increase 
of the brain weight with increasing body weight of the (domestic) 
albino Rat finds expression in the slower ascent of the curve and 
the lower value of the exponent. It may be admitted that the 
exponent is in general somewhat lower in the domesticated species 
(not leading a natural life), because the brain increases somewhat 


‘) E. Miitter, Vergleichende Untersuchungen an Haus- und Wildkaninchen. 
Loe. cit. p. 5083—588. 

4) See note 9 foregoing page. 

3) See note 10 foregoing page. 

4) H. BerucKe, Vergleichende Untersuchungen an Frettchen und Iltissen. [bid., 
p. 589—620. 

5) O. Timmann, Vergleichende Untersuchungen an Haus- und Wildenten. Ibid., 
p. 621—656. 

6) Donaupson and Harayl, l.c., p. 426—427. 

1) From Chart 31, p. 201 in H. H. Donatspon, The Rat. Reference Tables 
and Data for the Albino Rat (Mus norvegicus albinus) and the Norway Rat (Mus 
norvegicus). Memoirs of the Wistar Institute of Anatomy and Biology. N°. 6. 
Philadelphia 1915. 

8) Ibid, p. 208. 


240 


less under these circumstances, in proportion to the body weight 
grows. in a less degree than in the natural state. 


BRAIN 
WEIGHT }+—— 
INGR. | 


ce) 50 100 150 200 280 300 350 200 45G 


Fig. 4. 


In 1918 I found an exponent of 5/13 = 0,27, ie. of precisely 
half the value of the exponent holding for the relative brain weights 
from species to species, on comparison of the volumes of largest, 
i.e. of full-grown, homologous nerve or ganglion cells 
in relation to the body weights of adult animals of very different 
sizes, both of one species and of different species. Compare Tables I 
and I] ?). 

Though in the microscopical image of the grey cortex the nerve 
cells are placed as densely and are as unequal in size as the stars 
in the telescopic image of, the Milky Way, we may yet admit a 
relation between the average size of these cells and the size of the 
body, and look for the explanation of the relation. holding for the 
volume of the brain in the nerve cells, the elements from which 
the brain is composed. 

The exponent holding between the adult individuals of one and 
the same species, in the relation of the body weight to the brain 
weight, may now be distinguished as ontogenetic exponent from 


1) These Proceedings, Vol. XX, p. 1828—1334. There too the fuller references 
to the works of the authors mentioned in the last column of Table I. 


241 


the exponent holding from species to species, 
relative individual growth of the brain to the adult state. 
In consequence of this difference in 


the 


TA BERET 
| Body Nerve cell | 
| | Reference to authors, 
| weight Nee a2 | date and page of reported 
(grammes) “initra) | cription measurements 
| | | 
1, Elephas indicus 3600000 84.4 Col. ant. | 1. Hardesty. (1902). 160, 161 
2. Equus caballus 562500 61.9 t aes . 2 Rs 
- 3. Homo sapiens 72000 58.0 . aad bor i » 1595160 
4. Lepus cuniculus dom. A. 2000 39.2 5 Beans - » 160 
5. Mus norvegicus albinus. A 250 34.7 s lis . 5 A 
6. Mus musculus albinus 20 27.4 . ‘ > fs » 160, 164 
7. Lepus cuniculus dom. B 2000 56.0 Spin. G. Levi. (1908). 200 
8. Mus musculus. A 20 37.2 > ln » » ” 
9, Canis familiaris. A 23000 80.8 a ert » (1906). 331, 332 
10, Canis familiaris. B 3750 67.5 - - = a . = 
11. Mus norvegicus albinus. B 250 16.5 Purk. Addison. (1911). 469 
12. Mus musculus. B 20 13.0 = | Obersteiner. (1913). 5 
13. Felis leo 119500 69.5 max. Betz Brodmann. (1909). 83 
14. Felis pardalis 10433 66.5 med. n’ Bevan Lewis. (1880). 53 
69.0 max. is | Brodman (Lewis) (1909). 83 
15. Felis domestica 3300 
60.0 med. * Bevan Lewis. (1880). 85 


as it expresses the 


fixed relations of the 


weights of the brain and the body, between homoneuric species 
on one side, individuals of a species on the other side, i.e. the 
difference between the phylogenetic and the ontogenetic exponent, 
small individuals have comparatively more, large individuals compa- 
ratively less brain than species of corresponding mean body weight. 

This appears graphically in Figures 2 and 3. The difference ean 
become very great in dwarfs and giants of one species; it is very 
striking in the Figures 5 and 6, which give the accurate outlines, in 
natural size, of the skull of a medium sized fennec (Canis zerda), tle 
smallest species of the genus Canis, and one of the smallest 
individuals of the species Domestic Dog, of a diminutive breed, 


242 


T ACB EES Ul 


Calculated Values of the Exponent r for the Increase of the Volume 
of the Nerve Cells with the Body Weight 


Proportion 
Bee eten of the Exponent 

body weight 
1. Elephas indicus and Mus musculus albinus Col. ant. 180000 : 0.2789 
2. Equus caballus and Mus musculus albinus - i 28125: 0.2387 
3. Homo sapiens and Mus musculus albinus ‘ ‘ 3600: 0.2747 
4. Lepus cuniculus dom. A and Mus musculus albinus fy ; 100: 0.2333 
5. Mus norvegicus albinus. A and Mus musculus albinus = Zor 0.2805 
6. Lepus cuniculus dom. B and Mus musculus. A Spin. 100: 0.2665 
7. Canis familiaris. A and Canis familiaris. B = 6: 0.2975 
8. Mus norvegicus albinus. B and Mus musculus. B Purk. 12.5 0.2832 
9. Felis leo and Felis domestica Betz 36: 0.2804 
10. Felis pardalis and Felis domestica = a}s 0.2681 


probably a toy-terrier, of the same body weight, after photographs 
which | owe to Prof. W. Lecue at Stockholm. The brain weight 
in the diminutive individual of Domestic Dog, with only a ninth 
of the mean body weight of the species, is indeed quite 87°/, 
more than the mean of the smallest species of Canidae’). The 
amount and the plus or minus sense of this difference with species 
is dependent on their body weight. The smaller the species 
of the genus Canis, the more it is exceeded in brain weight by 
an individual of the same size of the Domestic Dog species. 
Domestic dogs of the size (the body weight) of the common (Kuro- 


1) The body weight of a female fennec, killed in its African home, was 1.5 kg. 
according to KLarr (Studien zum Domestikationsproblem, p. 36), the weight of 
the brain was 25.2 g. The capacity of an almost adult female skull in the Leiden 
Museum of Natural History, observed by me, was 20 c.c., of two other skulls, 
of which the sex is not indicated, in the Berlin Zoological Museum, the capacity 
observed by Kuarr, is resp. 20 and 18 c.c. When for the species 2 kg. body 
weight, and 27.9 gr. brain weight is assumed, this gives certainly about the true 
ratio; absolutely these weights are possibly estimated too high. From the observa- 
tions of Kiarr (tbid., Haupttabelle) on 17 adult toy-terriers (Zwergpinscher), of 
an average body weight of 3.11 kg., with 58.1 gr. brain weight, I calculate for 
2 kg. body weight of this diminutive breed the brain weight at 52.3 gr. 


243 


pean) Fox have only slightly more than 28°/, more brain weight 
than this small species. Very large domestic dogs, of about 40 kg., 


Fig. 6. Skull of a domestic dog of diminutive breed, in natural size. 


i.e. the mean body weight of the Wolf, have 25°/, less brain 
weight than this largest member of the Canidae’). 

It is now of great importance that the ontogenetic exponent is 
equal to the exponent indicating the relation of the body weights or 


1) Through comparison with two foxes from France and one wolf from America 
LaPicquE (loc.cit. p. 329) had already pointed out these differences in 1907. 
Afterwards Kuarr (lbid, p. 36) corroborated them with more numerous data 
through a comparison with the Jackal and the Wolf. According to Kiarrt’s 
records on ten (German) foxes (Ibid., p. 37) and eleven domestic dogs (Haupt- 
tabelle) of about the same size, 6.12 kg. may be taken for the body weight of 


244 


volumes to the volumes of homologous nerve organglion cells, 
both between adult individuals of one species and between different 
species. This confirms that, with increasing body weight, from adult 
individual to adult individual of one and the same species, only 
the volume of each nerve cell in the brain increases, but from 
species to species at the same time the number ofthese cells, and 
that the number does so in the same ratio as the volume increases, which 
had already been rendered probable by other facts. Comparison of 
the brain weight in function of the body weight between the two 
sexes') had led me to the result, on the ground of the measurements 
of the diameter of the muscle fibres by Bowman and by Scuwa.Be 
and Mayepa, and the observations of muscle weights by THEILRE, 
that the number of muscle fibres of Man is equal to that of Woman. 
From the comparison of the relative quantity of brain and muscularity 
of the Europeans and the Japanese it had appeared to me that the 
relatively Jarger volume of the brain and of the muscles of the 
latter finds its explanation, not in the different number of the neu- 
rones and the muscle fibres, but in the larger cross-section of the 
separate muscle fibres, larger separate volume of the nerve cells ’*). 
Hence, between Man and Woman, between the Japanese and 
the European, i. e. within the species of Homo sapiens, only the 
volume, not the number of the nerve cells and of the muscle 
fibres differ. 


the Fox, 52 gr. for its brain weight; the average body weight of the eleven 
domestic dogs is 6.6 kg., their average brain weight 68 gr. Hence with equal 
body weight, the latter brain weight is 28.4°/, more than for the Fox. Compa- 
rison of these dogs with the jackals (Canis aureus) leads to similar results. The 
average body weight of fourteen jackals according to KLarr’s observations (Haupt- 
tabelle) is 6.836 kg., their average brain weight 57.1 gr. The difference with dogs 
of the some body weight is 20.1 °/,, somewhat less than the difference of these 
with the Fox, because the cephalisation of the Jackal is a little higher. In contrast 
with domestic dogs of the size of these small Canidae, domestic dogs of the size 
of the Wolf have 24.8°/) less brain than averagely this largest species of the 
genus Canis. From Kuarr’s records (Haupttabelle) of brain weights of six and 
body weights of four Lapland and Russian wolves, and of cranial capacities of 
23 European and American wolves (Kiarr, Ueber die Verinderung der Schadel- 
kapazitat, p. 166), averagely 161 c.c., | derived a body weight of the species of 
40 kg., a brain weight of 147.6 gr. Absolutely both weights may be a little 
too high, relatively most likely they are about right. Accordingly the Wolf is 
about equal in its cephalisation with the Fox. But twenty dogs of Kuarr’s observa- 
tions, of 30 to 48 kg., averagely 37.6 kg. body weight, have an average brain 
weight of 109.4 gr. 

1) Under this title in these Proceedings, Vol. XX1, p. 868—869. (1919). 

®) Eve. Dusois, On the Significance of the Large Cranial Capacity of Homo 
neandertalensis. These Proceedings, Vol. XXIII, p. 1281. (1921). 


245 


From the still little known, but very important measurements of 
muscle fibres by von per Matspure ‘) the same may be derived for 
individuals of unequal size of different Mammalia. 

In Table [Il some individuals of five species, being in a fairly 
good condition, and of a body weight as different as possible, are 
compared as regards the relation between the latter and the eross- 
section of homologous muscle fibres. This cross-section appears to 
increase in direct ratio to the surface of the body, hence to the 
cross-section of homologous muscles, which means that the number 
of muscle fibres within a species does not change with increasing 
size of the body. Also the number of nerve fibres and that of the 
nerve cells of the brain may then be admitted as being the same 
within a species. 

This is certainly not the case between different species, for when 
the specific differences of caliber are taken into account, through 
which homologous muscle fibres of different species of animals (just as 
not homologous muscles of the same species) are distinguished, not 
much remains of a direct influence of the size of the body on this 
caliber of the muscle fibre. The number of the muscle fibres must, 
therefore, greatly increase with the size of the animal species. 
According to von pkr Matspure the average diameter of the muscle 
fibres in the rectus abdominis and the gastrocnemius is for the Ox 
45.88 micra (in its different breeds 35.35 to 63.37 micra), for the 
Horse 39.20 micra (breeds 33.26 to 48.60 micra), for the Pig 42 
micra, for the Sheep 22.61 micra (breeds from 18.50 to 30.85 micra), 
for the Goat 18.90 micra. For the average diameter of the muscle 
fibres in the gastrocnemius of the Dog (calculated from v. p. M.’s 
records, applied to the mean body weight of this species) 21 micra 
may be assumed, the average of four hares is 19.20 micra, and of 
five mice 17.40 micra, the body weights of these two last species 
being to each other as 200: 1. 

With not inconsiderable specific differences (but much smaller 
than between the different breeds and individuals), only small differ- 
ences between these species are to be ascribed to the influence of 
' the size of the body. Thus also Mayepa and Scuwatse*) found in 


1) Karot von per Matssure, Die Zellengrésse als Form- und Leistungsfaktor der 
landwirtschaftlichen Nutzliere. Arbeiten der Deutschen Gesellschaft fiir Ziichtungs- 
kunde. Heft 10. 367 pag. Hannover 1911. 

3) R. Mayepa, Ueber die Kaliberverhiiltnisse der quergestreiften Muskelfasern. 
Zeitschrift fiir Biologie. (KiiuNE und Voit). N.F. Bd. 9, der ganzen Serie Bd. 27, 
p- 129. Miinchen und Leipzig 1890. — G. ScuwaLse und R. Mayepa, Ueber die 
Kaliberverhaltnisse der quergestreiften Muskelfasern des Menschen.|bid,p. 487,489,515. 

16 

Proceedings Royal Acad. Amsterdam. Vol. XXV. 


TA BLE 


246 


III 


Relation of the Cross-Section of Homologous Muscle Fibres to the Body Weight, 
in Individuals of Different Sizes of one Species 


m 
= p Diameter of the Calculated 
as muscle fibres, in micra power of 
= Y Body 
oa Species oH nee P, which is 
Ww 
fo eign’, | Gastro- | apdominis propor- 
: in kg. | cnemius and ; 
o Gastro- |tionaltom? 
cnemius : 
| 
Horse 
146 4 heavy, average 712.5 46.16 
0.6459 
146 2 light -5 290 34.53 
102 Belgian male 850 49.60 
0.6750 
102 Pony, male 300 34.90 
102 5 males, average 740 48.79 
0.7218 
104 4 3 s 437.5 40.36 
Ox 
95 4 bulls, average 662.5 45.17 
0.6670 
97 3) ty ” 416.6 38.70 
95 Bos taur. primig. var. Sarm. 600 45.00 
0.6030 
98 » ” n ” ” 350 38.25 
Pig 
108 Wild, male 130 48.25 
0.7800 
108 » female 80 40.10 
149 Yorkshire 100 44.00 
0 5480 
much 
149 » dwarf (ermpertea) 11.8 24.50 
Dog 
109 Newfoundland (emaciated) 49 38.10 
0.7402 
109 Fox-Terrier 9 20.35 
Rabbit 
326 |Domestic, large breeds, average 3.3 36.65 
0.6946 
326 > small ; x 1.5 27.87 
Mean 0.6751 


247 


their measurements the muscle fibres in the gastrocnemius of a 
mouse about as thick as in the homologous muscle of a woman 
and of a dog (but thinner than in that of a man). In the masseter 
of their mouse the muscle fibres were about as thick as in the 
masseter of the man, but less thick than in the dog. That the size 
of the body from species to species has only little influence on the 
caliber of the muscle fibres appears also from this that G. Levi’) 
found the diameter of the thickest muscle tibres in the rectus femoris 
of a mouse not below that in a rat (twenty times as heavy). 

It may, therefore, be admitted that in homoneuric species the 
number of muscle fibres, and then also proportionally that of the 
ganglion cells in the brain, greatly increases with the size of the body. 
But the available data do not enable us to calculate the exact 
relation of the body weight to the number of the muscle fibres 
in these species. On the ground, however, on one side of the 
relation found for the brain weight F to the body weight P, 
according to which EZ increases proportionally to P%s between 
homoneuric species, and proportionally to P*s between adult indi- 
viduals of the same species, and on the other side, on the ground 
of the relation found for the volume of the separate nerve 
cells C to the body weight, according to which C increases in 
the ratio of P%is, both between individuals and between species; 
further on the ground of the established fact that between large 
and small individuals the number of the muscle fibres, hence 
proportionally that of the nerve cells in the brain, does not differ, 
but that it differs greatly between large and small species, we may 
conelude, that also the number of the nerve cells between 
homoneuvic species increases in the ratio of P*is. 

The difference between the phylogenetic and the ontogenetic 
exponent is thus rationally explained. It means that in the origina- 
tion of the species, increase of the size of the body is accompanied 
with multiplication of the nerve cells, through cell division (in non- 
homoneuric species this multiplication is greater in certain parts of 
the brain) ’). With the establishment of larger adult individuals 

1) Giusepre Levi, Studi sulla grandezza delle cellule. Archivio di Anatomia e 
di Embriologia. Vol. V, p. 327. Firenze 1906. 

2) Direct counting of the cells in the grey cortex of Monkeys by Orro Mayer 
(Mikrometrische Untersuchungen tiber die Zelldichtigkeit der Grosshirnrinde bei 
den Affen, Journal fiir Psychologie und Neurologie, Bd. 19, p. 237. Leipzig 1912) 
teaches that per m.m.*, calculated throughout the cortex, only about the same 
number of cells occur in the small Hapale (3448) as in the larger Chrysothrix 
(3603) and in the still larger Cebus (3581). As the brain weights in these hetero- 
neuric and from the smallest to the largest species higher cephalized American 

16* 


248 


of a species, there is no nerve cell division; these cells only increase 
in volume, which they also do with the origination of larger 
species. For this increase of the nerve cell volume is a mechanical 
necessity, as may appear further below. 

That phylogenetic increase of the volume of the brain is actually 
brought about by cell division, associated with equivalent increase 
of the separate cell volume, is also proved by the fact that in 
related, but heteroneuric species, with equal body weight, the volumes 
(or weights) of the brain or — what comes to the same — with 
inequal body weight, the caleulated coefficients of cephalisation, 
in many cases, are to each other as 1, 2, 3,4. The cranial capacities 
of the Chimpanzee (450 ¢c.c.), of Pithecanthropus (900 ¢.c.), and 
of the male Australian aboriginal (1850 ¢.c.) are to each other as 
the numbers 1: 2:3. The coefficient of cephalisation of the Man-like 
Apes is twice that of the Old World Monkeys and Baboons; Cebus 
has double the cephalisation coefficient of Cbrysothrix; in the 
Megachiroptera it is twice that of the Microchiroptera. The coefficient 
of the Tree Shrew (Tupaja) is four times that of the Common Shrew 
(Sorex) and the Musk Shrew (Crocidura). The coefficients of the 
genera Mus, Lepus, and Sciurus are to each other as 1:2:3. The 
genera Tapir, Sus, and Hippopotamus have a coefficient of cepha- 
lisation half as great as that of the Horses, the Deer, the Giraffe, 
the Antilopes, and the Oxen. The Chevrotain (Tragulus) also has 
a coefficient only half so great as the modern-type Ruminants. It 
is extremely interesting that among the Mustelidae, the Polecat 
(Putorius putorius), the Stoat (Putorins ermineus), and the Weasel 
(Putorius nivalis) possess a coefficient of cephalisation only half so 
great as the Beech-Marten (Mustela foina) and the Pine-Marten (Mustela 
martes). In this respect the Badger (Meles) agrees with the former, 
the Otter (Lutra) with the latter group. 

We meet here with an important phenomenon, analogous to the 
“narameter-law” of crystals, and, undoubtedly, intimately connected 
with the polyploidy of nuclei and consequent rational inerease of 
cell volume. 

It may, further, be pointed out that most of the heteroneuric 
species mentioned with low cephalisation, are small, in comparison 
with the allied species with high cephalisation. This proves that the 
phylogenetic growth of the brain, in which — different from what 


Monkeys are to each other as 8:24:70, the absolute number of cells increases 
considerably more than would correspond with the same size of body of homo- 
neuric species. In the nearly homoneuric Gibbon (Siamang) and Chimpanzee those 
numbers are 3160 and 1765, and the brain weights to each other as about 1:3. 


249 


is found in the establishment of a new homoneuric species — certain 
parts of this organ increase to a greater degree than the other parts, 
and accordingly a heteroneuric species originates, is probably always 
too accompanied with increase of the bulk of the body. Only with 
the same increase of the bulk of the body, the increase of the 
volume of the brain is comparatively greater than in the establishment 
of a new homoneuric species. 

Another peculiarity of the Polecat may be considered in connection 
with what has been said about its lower cephalisation. When 
with the observations of weight of the body and the brain by 
Betucke') of ten certainly adult polecats, the ontogenetic exponent 
is calculated, from the five with body weights above 1000 gr. 
(average 1281.5 gr.) and the five under 1000 gr. (average 769 er.), 
0.42 is found for it, the same value as is obtained from the weights 
of a very large polecat (of 1700 gr.), from the observations of 
Lapicqur’), and a very small one (of 593 gr.), of my own obser- 
vations’), both adult animals. This exponent is exactly halfway 
between °/ig and °/9. In a graph the direction of the ontogenetic line 
of the Polecat would be seen to deviate from other ontogenetic lines, 
and approach to coincidence with the phylogenetic line of the genus 
Putorius. Evidently the species of Polecat is in a state of disintegration. 
Probably the other Putorius species are too. Well-known is, indeed, 
the great variability of all the species of this genus. 

In the ontogenetic growth there is an important difference between 
the nerve cells and the other cells of the body. It is the great 
merit of Giuseppe Levit and of Epwin Conkuin to have pointed this 
out. In 1906 Levi‘) proved for a great number of Mammalia and 
in 1908 for the Vertebrates in general‘), that in contrast with most 
cells, except probably the muscle fibres (and those of the crystalline 
lens), the size of the nerve cell increases with the size of the 
animal"). The other cells increase in number, not separately in size. 


1) Loe. cit., p. 613. 

2) Comptes rendus. Académie des Sciences. (2), Tome 151, p. 1393. Paris 1912. 

§) Verhandeling of 1897, p. 36. Also: Bulletins de la Société d’Anthropologie 
de Paris, 1897, p. 371. 

4) Loc. cit. 

5) GiusepPE Levi, | Gangli cerebrospinali. Supplementa al Vol. VII dell’ “Archivio 
Italiano di Anatomia e di Embriologia’’. Firenze 1908. 

5) Irving Harpesty, already in 1902, found that the size of the motor nerve 
cells from the spinal chord of various Mammals increases with the size of the 
body. (Observations on the Medulla spinalis of the Elephant with some Comparative 
Studies of the Intumescentia Cervicalis and the Neurones of the Columna Anterior, 
Journal of Comparative Neurology. Vol. XII, p. 125 seq. Philadelphia 1902). 


250 


In 1912 Conkuin') showed for different species and individuals of 
one species of Boat Shell (Crepidula), that in spite of the very great 
differences in body size, ‘the size of tissue cells is approximately 
the same in all species examined, and in all individuals of both 
sexes and of very different sizes. In the main, differences in body 
size are due to differences in the number of cells present, and not 
to variations in the size of individual cells. Ganglion cells and muscle 
cells form the principal exception to this rule’. (According to his 
measurements the diameter of muscle fibres is not greater in the 
larger species, and only a little greater in large-sized individuals of 
one species). From his measurements of a gigantic female and a 
medium-sized male individual of Crepidula plana I find for the 
exponent of relation of the volume of the body and the volume of 
the ganglion cells the value of 0.3149, whieh is sufficiently near 
5/13 to prove the existence of the same ontogenetic relation also in 
the Invertebrates. 

As was already mentioned, Levi is less certain in his conelusion 
about the muscle fibres; he generally finds them thicker in large 
animals than in small ones, but the thickness changes much less 
than the length, and there are many exceptions to the rule. This 
uncertainty is, indeed, explicable by what was derived above from 
von prER Maxspure’s measurements with regard to the larger differ- 
ences between individuals than between the species. 

The nerve cells and the muscle cells are distinguished from 
most other cells (only the fibres of the ervstalline lens make an 
exception to the general rule) in that early in life — in Man and all 
Mammalia examined on this point about birth-time — they cease 
increasing in’ number through division, but then continue for some 
time to increase separately in volume. The other cells go on multi- 
plying by division throughout life. The musele cells continue increas- 
ing their separate volume at least up to the adult state of the 
individual. But the. nerve cells also stop doing this in the early 
youth of the individual. 

A consequence of this peculiarity of the nerve cells is, that 
early in the life of the individual the brain assumes the volume of 
the adult state of the body; in a male child for instance, at the 
age of nine, in a female child when six years old. But a similar 
remark holds among others for the Dog, the Rat, the Great Ant- 
Kater, the Sparrow, the Chicken, the Crocodile, the Frog, the Salmon, 


1) Epwin G. Conky, Body Size and Cell Size. Journal of Morphology. Vol. 23, 
p- 159—188. Philadelphia 1912. 


= 


251 


in short for all the Vertebrata, and also for the Invertebrata. At 
birth the brain weight of Man is !/s, and in the adult state of the 
body 1/s; of the body weight. At its birth a dachshund has 1/9, and 
in the adult state 1/,35 of its weight in brains. With a body weight 
of 7 grams the Brown Rat has less than 1/49, and when it is full 
grown !/i¢69 of its weight in brains. In the Bull Frog of 4'/, grams 
of body weight, the brain weight constitutes '/jo9 of it, and when 
the body weight has increased to 200 grams, the ratio of the brain 
weight is only 1/1990. This gives the skulls, of them all in their first 
youth, a much more humanlike appearance than they have in the 
adult state. The great resemblance of the skull of young Apes with 
that of Man cannot, therefore, have the special significance that is 
sometimes ascribed to it. 

The peculiarity of the nerve cells manifested in this early cessa- 
tion of cell division in the ontogenetic growth, now accounts also 
for the long interruptions in the phylogenetic growth, (also resting 
on cell division), especially if this growth is stronger in certain parts 
of the brain and mostly in those with the highest integrative action. 
This phylogenetic growth then takes place with long intervals, as 
shown anatomically in the brain quantities of allied heteroneuric 
species of the present animal world, paleontologically by comparison 
of animal forms of the present time with those of a former world order. 

But why arethe nerve cells distinguished in this conspicuous way 
from all other cells, with the exception of the muscle cells, which 
act under their influence? We find the volume of the nerve cells to 
be in a particular, in what precedes not yet causally explained relation 
to the body weight. What is the meaning of that “strange” °/13 power? 
To a proportionality with the ®/;s or '/3 power of the body weight, 
i.e. with the linear dimension of the body, we could readily ascribe 
a dynamic significance; as the mass of the body increases as P, 
the physiological cross-sections of the muscles, which determine 
the muscular force, the sensual areas, the areas that determine 
metabolism increase only proportional to P*s, it would be compre- 
hensible if this inadequacy implied an increase of the volume of 
the nerve cell proportional to P's. But this takes place in a definite, 
smaller proportion, according to P*is. 

In order to detect the meaning of this latter proportionality | 
examined on a former occasion ') in what relation the volumes of 
the principal constituents of the nerve cell, the nucleus and the 
plasma, are to each other and to the body weight. The result 
of this examination is recorded in Table IV. 


_ 1) These Proceedings, Vol. XXII, p. 671—675. (1920). 


252 


nA BLE 


Calculated values of the exponents a, 2 (= 5/;3d@) and & for the increase of the 
plasma volume D with the cell volume C and with the body weight P, and of 
the nucleus volume K with the cell volume C. (From measurements of the diameters 
of ganglion cells and their nuclei by Giuseppe Levi, and corresponding linear 

dimensions of their plasma). ') 


: : d in A in k in 
Situat f tk 
Species iba tie : - oa Py ORY TG 
ganglion cells G mpi P, Dj G mnK, 
1. Bos taurus, 1 and Mus 
musculus, 8 Gangl. spin. 1.198 0.3327 0.5348 
2. Bos taurus, 2 and Mus 
musculus, 8 id id. 1.203 0.3342 0.5268 
3. Lepus cuniculus, 4 and Mus 
norvegicus, 7 id id. 1.202 0.3338 0.5987 
4. Lepus cuniculus, 4and Mus 
musculus, 8 id id 1.206 0.3351 0.6143 
5. Mus norvegicus, 7 and Mus 
musculus, 8 id id. 1.210 0.3362 0.6288 
6. Cavia cobaia, 5 and Arvi- 
cola arvalis, 9 id. id 1.216 0.3378 0.6703 
7. Cavia cobaia, 6 and Arvi- 
cola arvalis, 9 id id. 1.259 0.3497 0.6025 
8. Felis domestica, 10 and 11, 
gin. cerv. V and cocc. I id. id 1.123 03119 0.6466 
9. Python (species), 12 and 
Seps chalcides, 14 id id. 1.187 0.3296 0.5892 
10. Varanus arenarius, 13 and 
Seps chalcides, 14 id. id 1.203 0.3341 0.5386 
11. Bos taurus, 15 and Mus 
musculus, 16 Rad. ant. spin. 1.195 0.3320 0.6555 
12. Canis familiaris, 17 and 
Canis vulpes, 18 Purkinje cerebell. 1.199 0.3330 0.6651 
13. Canis familiaris, 21 and Gangl. cerv. sup. 
Putorius putorius, 22 n. sympath. 1.248 0.3466 0.6523 
Mean 1,204 | "0.3344 0.6095 
The cells compared there are all adult, and homologous as regards 
their general character, but not being in each case of accurately 
corresponding places in the central nervous system, they cannot be 


directly referred to the body weights. 


') Cf. in these Proceedings, Vol. XXIII, p. 672, Table I. There on p. 674 also 


the above calculations were already published in Trble Il. 


253 


When now the power of the cell volume C, is calculated, by 
which the plasma volume JD increases, we find for it 1.2 or ®/s. 
We find 0.6 or 3/5 for the power of the cell volume by which the 
nucleus volume XK increases proportionally. On increase of the nerve 
cell the plasma volume varies, therefore, proportionally as the square 
of the nucleus volume. As °/5  °/1g = /ig or 1/3, the plasma volume 
appears to increase proportional to the third root of the body weight 
or P':, and the nucleus volume proportional to the sixth root of 
the body weight or P'hs. 

Thus it appears that only the plasma, which is directly connected 
with the nerve fibre, in such a way that the axis cylinder passes 
into it, has the said direct dynamic significance. The nucleus, which is 
always separated from the plasma by a membrane, is directly concerned 
only with the life of the cell and its intern mechanism. The nucleus, 
in the common opinion, is the bearer of the hereditary properties 
in the nervous system, and it regulates the constructive metabolism, 
growth, and reproduction of the cell. 

But still this ‘strange’ exponent °/ig is only partly accounted 
for. Why does the volume of the nucleus A vary proportional 
to the sixth root of the body weight, i.e. to the square root of the 
body length, VL, or K* to L? 

This too I already discussed on that former occasion. The follow- 
ing remarks may now be added. 

It has appeared chiefly from the then cited cytological researches 
and studies by Gerassimow, Bovert and R. Hertwie that the volume 
of the plasma depends on that of the nucleus: The relative size of 
the nucleus is determined by a dynamic state of equilibrium between 
the volume of the nuclear substance and the free surface of the cell, 
i. e. of the plasma. Further that with such a constant ratio the rate 
of cell division also remains constant. Now we actually see in the 
largest, i.e. full-grown homologous ganglion cells, in every case com- 
pared above, the volume of the nuclear substance increase in nearly 
quite the same relation with the body weight as the free surface of 
the cell, for Ps = P%: and P*sxX%s — Ps, It may, therefore, be 
admitted that these cells are in such a dynamic state of equilibrium. 
The volume of the nucleus increases, indeed, somewhat less than 
exactly proportional with the surface of the cell (which would be 
required for cell division), but in this condition of the cell it remains 
in equilibrium with the general dynamic condition of the body. For 
the metabolism of the cytoplasma increases in the same rate with 
the increasing volume of the nuclear substance A, and consequently 
the kinetic energy issuing from the nucleus proportionally to A’. 


254 


Bat we found also K? increasing proportionally to LZ or P%s. And 
this is the same ratio as exists between the mass of the body and 
the muscular force, the metabolism, the rate of conduetion of the 
nerve impulses. 

It has been found eytologically that with constant relation of 
nucleus and plasma also the rate of cell division remains con- 
stant. And already in 1895 Atexanper SurHerLAND') had shown that 
the time of incubation of bird species and the time of gestation of 
related species of mammals increases proportional to Ps or VL; 
weight and length being those of the full-grown animal’s body. 


In general this time is Ty P, in which n is a constant, 
almost the same for all bird species, but different for every order 
or family of the Mammalia, which tends to inerease with the 
increase of “nerve complexity, as gauged by size and efficiency of 
”. Its amount is in indubitable connection with that of the 
coefficient of cephalisation x, which is determined by the hetero- 


brain 


neuric increase of the number of nerve cells; but m certainly 
increases less greatly and is, in Mammalia, also dependent on other 
circumstances (as the non-coincidence of the dates of copulation 
and fecundation). The values nm and x are highest in Man, Apes, 
and the Elephant. The i05 bird species mentioned by SuTHuRLAND 
differ relatively little inter se in their cephalisation, but in some its 
influence on the time of incubation can yet be recognized, such in 
the Owls in comparison with the Gallinae. Thus the time of growth, 
determined by cell division, to birth appears to be in the same 
relation to the body weight of the adult animals as the nucleus 
volume of full-grown homologous nerve cells, which cease dividing 
at birth. This means equal increase of the number of nerve cells 
to their separate volume. Again, finished cell division in the brain 
implying completion of linkage in the nervous integrative machinery, 
it thereby causes mechanically birth, of mammal as well as bird. 

In the origination of a heteroneuric species the phylogenetic 
growth of the brain volume is not uniform, in simple mechanical 
accordance with the phylogenetic growth of the body, as in the 
establishment of a larger homoneuric species, but it is stronger in 
those most compounded parts of the brain, where new chains of cells 
are superposed upon the preéxisting chains, superiorly integrating 


1) ALEXANDER SUTHERLAND, Some Quantitative Laws of Incubation and Gestation. 
Proceedings of the Royal Society of Victoria. Vol. VII. (New Series), p. 270— 286. 
Melbourne 1895. Also in The Origin and Growth of the Moral Instinct, p. 69—71 and 
101—102. London 1898. 


255 


parts upon the inferiorly integrating parts of the brain. Yet the brain 
volumes, corresponding to equal body weights, of heteroneuric species 
are to each other as 1 to 2, 3 or 4, which implies that the volume 
of those superposed chains of cells, in the origination of a heteroneuric 
species, is equal to, double or triple the volume of the preéxisting 
chains. We may infer from this, that the phylogenetic progress of 
the brain, by evident discontinuous variation (mutation), after all 
depends on segregation of aliquot parts from polyploidly increased 
nuclear substance. 

As, again, the size of the nerve cell body and its chief component 
parts is adjusted to the mechanism of the whole animal, and every 
nerve cell is bound to codperation with many homologous, 
and non-homologous nerve cells, its relatively stable character, 
manifested in the ontogenetically limited, and phylogenetically in- 
frequently, but then from the beginning definitely increased multi- 
plication by division, becomes comprehensible, especially when — 
in the origination of a heteroneuric species — the multiplication 
must be greater in the most compounded and intricately functionating 
parts of the brain. 


Physiology. “A further Contribution concerning the function of 
the Otolithic Apparatus.” By Prof. R. Maenus and A. pe KLEyYN. 


(Communicated at the meeting of May 27, 1922). 


In a previous publication ') we demonstrated that when caviae are 
centrifuged by Wirrmaack’s method, being thereby deprived of otolithie 
membranes, the labyrinth-reflexes resulting from position (tonic 
labyrinth-reflexes on the extremities, “Labyrinth stell-reflexes”, and 
compensatory eye-positions) will disappear, but that, on the other 
hand, the labyrinth-reflexes responding to’ movement (rotatory actions 
and after-reactions on head and eyes and the reflexes on progression- 
movements) will persist. It follows that the above position labyrinth- 
reflexes are otolithie reflexes, since change of position of the head in 
space does not enable us to elicit a change of the stimulation in the 
sensory epithelium of the otolithic maculae, but does not at all 
mean that the sensory epithelium cannot, under these circumstances, 
be in a permanent condition of stimulation. It is a priort quite 
possible that the sensory epithelium of the maculae, like that of the 
retina, continually produces stimuli, whose magnitude, in the absence 
of the removed otolithic membranes, can no more be altered by the 
changes of position of the head in space. 

This conception was brought home to us by experiments to be 
published afterwards. 

In order to go further into this subject we started from the 
following consideration : ; 

The extirpation of one labyrinth in a normal animal brings about 
an intricate complex of phenomena. A previous minute inquiry ’*) 
into these phenomena enabled us to establish the following symptoms 
as resulting directly from the unilateral extirpation, of the otoliths 
(membranes ++ sensory epithelium) or rather from the activity of 
the otolithic Organs on one side only : 

a. Rotation and flexion of the head towards the missing labyrinth. 

b. Hye-deviation: the eye on the side of the removed labyrinth, 
deviating downwards, the other upwards.. 


1) These Proceedings, Vol. XXIII, p. 907. 
*) Pfligers Archiv. 154. 178. (1913). 


257 


As secondary results from the rotation of the head sub a appear 
change of posture of the whole body, difference of tonus in the 
extremities, rolling movements ete. 

We do not know as yet which part of the labyrinth is responsible 
for a transitory difference of tonus in the extremities, which persists 
also with the head in the normal position towards the trunk. This 
symptom has, therefore, to be left out of consideration in the 
following discussion. 

On the basis of these findings we performed the following expe- 
riments : 

Caviae were centrifuged after the familiar method of Wirrmaack. 
Now only those animals were used for further experimentation in 
which clinically all labyrinth-reflexes of position disappeared and all 
movement-reflexes maintained themselves, or, in other words, animals 
in which it could be expected that all the otoliths had been completely 
detached on either side. 

In order to eliminate as much as possible a_ stimulating, or 
paralysing influence of the removal itself on the sensory epithelium, 
the animals were regularly examined and the experiment proper 
was started only from 7 to 9 days after the centrifugation. 

In this procedure about 0.1 ec. of a 5°/, cocain solution was 
injected unilaterally through the ear-drum into the middle-ear, in 
order to paralyse the whole labyrinth on that side. 

If it should now appear that, after the removal of the otoliths, 
the sensory epithelium of the maculae was not in a condition 
of stimulation, it could be expected that no phenomena should reveal 
themselves after the cocain injection, with the exception only of a 
nystagmus consequent on the elimination of the semicircular canals 
on the injected side. 

If, however, there is indeed, after the removal of the otoliths a 
stimulation in the sensory epithelium of the maculae, we may look 
for asymmetrical phenomena after the cocain-injection, since at the 
injected side the sensory epithelinm is completely paralysed and there 
is a constant condition of stimulation at the other side. 

After the cocain-injection a rotation of the head towards the 
injected side (“Grunddrehung”’; utriculus) and an eye-deviation (eye 
at the injected side down, the other eye upwards; sacculus.) may 
then be expected, i.e. phenomena agreeing with those appearing in 
normal animals, if ipsilaterally the labyrinth is paralysed through 
extirpation or through injection. With this difference, however, that 
the phenomena in animals with removed otoliths do not vary, as 
is the case in normal animals after unilateral extirpation of the 


labyrinth, 


258 


with the various positions of the head in space consequent 


on the varying influence of the otoliths of the unimpaired side, but 
that these phenomena are constantly the same whatever the position 
of the head of the animal under examination may be, when it is 


held up freely in the air. 
Five similar experiments were made, which are instanced in the 
following three protocols: 


28/6 1921; 


2/7 1921: 


4/7 1921: 


5/7 1921: 


11h 39’. 


11h 41’, 


11h 43’. 
11h 47’. 


11h 49’. 


11h 51’, 


11h 54’. 
12h, 


12h 3’, 
12h 6’. 


Cavia R: 


All labyrinth-reflexes normal. 

Centrifugation: head up, chest inward, time 2 minutes, rate 1000 m. 
per minute. : 

Total lack of tonic reflexes. 

Reflexes of the semi-circular canal: rotation-reactions towards the 
right positive, to the left weak. 

Progression-reactions: doubtful or lacking. 

Total lack of tonic reflexes. ; 

Reflexes of the semi-circular canal (also progression-reactions) all 
present and symmetrical. 

Tonic reflexes: all present. Sits symmetrically, no eye-deviations. In 
dorsal position with head in normal position to the trunk ; no distinct 
difference of tonus in the extremities. 

0.1 ce of 5°/) cocain solution into left middle-ear. 

Held up in the air with head down: head 90° towards the right. 
When sitting OD').down OS *) up (consequently stimulation of the 
left labyrinth). 

Head down: head symmetrical again. 

Head down: head 20—80° rotation to the left, slightly turned to the 
left. When sitting a slight levoversion of the head, no distinct eye- 
deviations. 

Head down, 45° levo-rotation. When sitting falls on the left side. 
Head in normal position: no distinct difference of tonus in the 
extremities. If moved on the grouna to the right much greater resi- 
stance then against moving to the left, strong inclination to the left 
(incipient paralysis of the left labyrinth). 

Head down: 70° levo-rotation. When sitting head-nystagmus towards 
the right. [s moved on the ground: rolling to the left. No distinct 
eye-deviation. 

Head down 90° levo-rotation. OS slightly downwards. OD upwards. 
OS weak nystagmus beats anteriorly upwards. OD posteriorly down- 
wards. No change of the phenomena with a change of the position 
of the head in space. 

Marked spontaneous nystagmus, direction as at 12h. 

Marked deviation and nystagmus, do not change with a different 
position of the head in space. 


1) OD means Right eyeball. 
2) OS means Left eyeball. 


6/7 1921: 


12h, 


28/6 1921: 


4/7 1921: 


7/7 1921: 


Injection 
12h 30’. 


12h301/,’. 
12h31/, 


12h311/y 
12h33’, 


12h 34’. 
12h 341/,’, 


12h 36’. 


12h 38’. 
12h 40’. 


12h 52. 


259 


Reflexes of the semicircular canal: all present and symmetrical. 
Tonic reflexes: all absent, asymmetry of cocain-test quite disappeared. 
Decerebration, fair stiffness. 

Shifting from ventral to dorsal position: no trace of tonic labyrinth- 
reflexes. Rotation of the head in lateral position: Typical cervical 
reflexes, no labyrinth-reflexes. 


Cavia WS. 


All labyrinth reflexes present and normal. 

Centrifugation: head up, chest inward, time 2 minutes, rate 1000 m. 

per minute. 

Reflexes of semicircular canal: asymmetric reflexes. Rotation-reactions 

on head and eyes with rotation to the right weak, with rotation to 

the left strong. 

Progression-reactions: weak; extension of the legs even lacking. 

Tonic reflexes: lacking, only slight ,,@runddrehung”’ to the left. 

Reflexes of semicircular canal: present and symmetrical. Progession- 

reactions weak but present. 

Tonic reflexes: lacking, no more ,Grunddehung’’. Sits symmetrically. 

No eye-deviation. 

Dorsal position head in normal position towards the trunk; no diffe- 

rence of tonus in the extremities 

of cocain in the left middle-ear. 

Held up in the air, head down: dextro-rotation of head (stimulation 

of the left labyrinth). 

Head down: head, in normal position, not turned. 

Head down: levo-rotation of the head (incipient paralysis of left laby- 

rinth). 

Head down: 60° levo-rotation of the head. 

When sitting, head turned and flexed to the left: clock-hand move- 

ments to the left, no nystagmus. 

OS downward, OD upward; no nystagmus. 

Marked eye-deviation, no nystagmus: no difference of deviation with 

change of position of head in space. Head down: head turned 90° 

to the left. 

Right lateral position : head in position 

of normal sitting animal. 

Left Jateral position: head in dorsal 

position. 

Dorsal position: head right lateral pos. 

Head up: head left lateral position. 

No nystagmus. 

Rotation to the right and to the left: eye-rotation reaction and nystagmus. 
5 e Fs >» »  » : head rotation reaction spositive. 

On the ground: clock-hand-movements to the left; pushed with expe- 

rimentator’s foot: rolling once to the left. 

Evident eye-deviation: for the first time very strong spontaneous ny- 

stagmus, OS anteriorly upward, OD posteriorly downward. 


No change of the rotation 
of the head with different po- 
sition of the head in space. 


4h, 


8/7 1921: 
9/7 1921: 


28/5 1921: 


31/5 1921: 


2/6 1921: 


5h 12’. 
6 hour. 


6h 2/, 


6h 6’. 


6h 7. 


6h 10’. 


260 


When sitting, head flexed and with maximum rotation to the left, 
marked rolling movements, strong spontaneous nystagmus. 

Tonic reflex entirely lacking. Yesterday’s asymmetry quite disappeared. 
Animal dyspnoeic. Decerebrate rigidity not good. 

Tonic labyrinth reflexes decidedly not present. 


Cavia F. 


All labyrinth-reflexes positive. 
Centrifuged with head up, chest inward, time 2 minutes, rate: 1000 
m. per minute. 
Semicircular canal reflexes: Rotation-reactions and after-reactions: 
positive. 
Progression-reactions: lift-reaction positive, the others weak. 
Tonic reflexes: lacking. 
Reflexes of semicircular canal: all positive. Tonic reflexes: lacking. 
0,05 ce. 10°/) cocain through left tympanum. 
Sitting with head placed in tbe normal position: OD upward, OS 
downward (incipient paralysis of left labyrinth). 
Sitting with head turned a little towards the left, the whole animal 
inclines to the left. 
Hanging with head down: ‘Grunddrehung” 90° to the left. 
Rotating with head inward, rotating to the left, weak rotation-reaction 
of the head, distinct after-reaction Dextro-rotation: marked rotation- 
reaction of the head and no after-reaction. 
Eye-rotation reactions: dextro rotation, distinct reaction with nystagmus, 
no after-reaction. With levo-rotation: reaction and afterreaction. 
Progression-reaction: Liftreaction not distinct. 

“Springing reflex” positive. 

Muscular tremor: positive in all directions except posteriorly. 
Tonic labyrinth-reflexes negative. 
Position of the head in the air with: 

Right lateral position: head in normal position 
to the trunk through ‘Grunddrehung”, often 


hangs down. 
g Ergo constant 


rotation of the 
| head, which does 
not change with 
change of position 
ofthe headinspace. 


Left lateral position: head in dorsal position 
through “Grunddrehung”’. 

Head up: head in left lateral position, animal 
now becomes restless (cocain-action). 

Head down: head turns 90° to the left. 

Dorsal position: head in right lateral position. 
through levorotation, often also in dorsal position 
with left flexion. 

When sitting with head placed in the normal position: OD anteriorly 
upward, OS posteriorly downward. Nystagmus just the opposite way. 
Right lateral position: OS posteriorly downward, nystagmus the 
opposite way. Eye-deviation and nystagmus of the left eye are the 
same with right and left lateral position of the head and equally 


strong; the same holds good also for OD. 
' 


261 


7/6 1921: Animal sits symmetrically, no eye-deviation. 
Reactions of semicircular canal: all positive. 
Tonie reflexes: all lacking. Asymmetrical phenomena quite gone as 
in cocain-test. 

8/6 1921: Like previous day. When sitting, head sometimes turned very slightly 
to the right, for the rest animal sits symmetrycally, no eye-deviations. 


Anatomical examination by Dr. M. ng Buruer. All otolithic membranes detached. 


Right sacculus; sensory epithelium without membrane; the otolithic membrane 
isolated in the sacculus between ductus endolymphaticus and the 
back-part of the sensory epithelium. 

Right utriculus; sensory epithelium without membrane; the otolithic membrane lies 
between the posterior portion of the macula and the entrance to 
the crus commune. 

Left sacculus; sensory epithelium without membrane: the otolithic membrane 
rests against the lateral wall of the sacculus and above the macula. 

Left utriculus: sensory epithelium without membrane; the otolithic membrane 
is detached towards the inner side and above the macula but lies 
in the utriculus. 


These experiments go to show that for more than a week after 
the removal of the otolithic membranes the sensory epithelium is still 
in a constant condition of stimulation. When one labyrinth is for 
some time eliminated by cocain, the stimuli emanating from the 
non-injected labyrinth will induce asymmetrical phenomena, similar 
to those after unilateral extirpation of the labyrinth in normal 
animals, with this difference, however, that in the centrifuged 
animals injected unilaterally with cocain, these phenomena do not 
change with a change of position of the head in the air. 

Considering that there was a week’s wait after the centrifugation, 
it is probable that the above condition of stimulation should no 
longer be ascribed to centrifugation, and that, therefore, to the 
sensory epithelium of the maculae the power should be assigned of 
eliciting stimuli, which, owing to the absence of the otolithic mem- 
brane, do not vary much as to strength. 

The function of the otolithic membranes, then, consists in altering 
the intensity of this condition of stimulation of the sensory epithelium. 
This stimulation will be stronger or weaker according as the mem- 
branes pull at the epithelium or press upon it. 

Relative to the portion of the sacculus (the main part) innervated 
by the N. saccularis it has been previously demonstrated that the 
stimulation decreases with pressure and increases with pulling. This 
mechanism exists probably also for the utriculusmaculae. 

17 

Proceedings Royal Acad. Amsterdam. Vol. XXV. 


262 


It appears that for the division of the sacculus (sacculus corner) 
innervated by the N. utricularis the relations are more intricate. 

Our results may perhaps be conducive to the proper conception 
of the function of the sensory epithelium of the otolithic maculae. 

The above-named property of the otolithic apparatus to elicit 
continuous stimuli even after the otolithic membranes are detached 
— as here described — undoubledly demands attention in the 
further study of the unilateral affection of these organs. 


From the Pharmacological Institute of the 
Utrecht University. 


Geology. — ,,Cuba, The Antilles and the Southern Moluccas.” By 
L. Rorren. 


(Communicated at the meeting of May 27, 1922). 


In 1865 E. Suess endeavoured to show in which way North-, 
and South-America are connected geologically '). Basing upon the then 
scant geological literature of the borderlands, he partly adopted the 
conceptions of some few of the older explorers. He observed that 
the mountain systems of Western North-America do not directly 
merge into those of Western South-America, but that in South- 
Mexico and in Guatemala the coastal ranges bend round, ramifying 
there in different chains, which cross transversely the narrow Central 
America, to proceed on their course in the Greater Antilles. All 
along the row of the Antilles Suxss imagined to observe the traces 
of a large chain of folded-mountains, which he conceived to extend 
along the North Coast of South America, as far as the boundary of 
Venezuela and Columbia to merge there into the Andes. So he 
considers the Andes of South-America as a continuation of the 
mountains of Western North America, but looks upon the curving 
chain of mountains via the Antilles as the connecting link. 

In the region of the Antilles Suzss distinguished three zones: an 
interior zone of small islands all composed of young volcanic rocks 
with very young coastal limestones and allied formations, extending 
from Grenada to Saba; a middle zone, in which in many places 
older, folded rocks emerge, building up the Antillean-Cordillera 
proper, extending from Trinidad via Barbados as far as Haiti, 
branching out there in at least two chains, of which the southmost 
proceeds via Jamaica to Honduras, while the most northern runs 
via Cuba to Yucatan; lastly an exterior zone, stretching from 
Barbuda via the Bahama Islands and Florida to Yucatan and which 
is supposed to be the remainder of the unfolded and disrupted 
“Vorland” of the Antillean Cordillera. 

Already Surss had pointed to the striking analogy between the 
row of the Antilles and the Southern Moluccas. A few years later 


1) E. Sugss, Das Antlitz der Erde. I. 1885. 


264 


this analogy was discussed further by Wicamann *) and Martin ?). 
In the Southern Moluecas we also distinguish an interior curve of 
volcanic islands, an intermediate curve, consisting of the remains of 
folded mountains, and farther to the east the remainder of the almost 
undisturbed ‘Vorland”’. 

In many points the hypothesis of Surss has been corroborated 
by subsequent researches. K. Sapper*) has demonstrated that the 
peculiar curvature and ramification of the. tectonical units in 
Northern Central America, which Suxzss only suspected, really exist. 
W. Stevers*) has proved it to be probable that the eastern Corde- 
rillas of Columbia split up in the North into different branches, 
then bend round to the North-east and to the east, and can be 
traced as far as Trinidad with rather great distinctness. Lacroix °) 
found in young voleanic rocks of Martinique xenoliths of mica- 
schist, proving thereby that in the subsoil of this island there still 
must exist old, metamorphic sediments. H6GBom has pointed out the 
remarkable analogy’) between the eruptive rocks of the Virgin 
Isles and those of the Andes of South-America. In the collections 
of the chemist Richarp Lupwie W. Sievers has found a young 
eruptive rock from Alta Vela, a small island south of Haiti, and 
has proved the possibility that this islet may be the continuation 
of the voleanie interior curve of the Lesser Antilles”). Finally 
W. Beret *), who arranged the above-named collections petrograph- 
ically, has shown the occurrence of old schists in Haiti. Lastly 
bE La Torre’) discovered in Western Cuba a fauna of Malm- 
ammonites and M. SancnEez Rore'®) established that this fauna bears 
a close resemblance to the jurassic fauna of San Pedro del Gallo 
in Mexico, which has been treated in such a masterly way by 
BurckHArDT"'), ; 

On the other hand Surss’s theory has not been universally accepted 


1) CG. E. A. WicumMann, Sammi. Geol. Reichsmus. II, 1887, p. 198 sqq. 

2) K. Marvin, Tijdschr. Kon. Ned. Aardr. Gen. VII, 1890, p. 260 sqq. 

5) K. Sapper, Peterm. Geogr. Mitt. Erg. Hefte 127, 1899, 151, 1905; Report 
8th Int. Geogr. Congr., held in the Un. States, 1904. 

4) W. Sinvers, Peterm. Geogr. Mitt. 1896, p. 125 —129. © 

5) A. Lacrorx, La Montagne Pelée et ses éruptions, 1904. 

6) A. Héasom, Bull. Geol. Inst. Upsala, VI, 1905. 

7) W. Srevers, Zeitschr. Ges. fiir Erdkunde Berlin, 33, 1808. 

8) W. Beret, Abhandl. Gesellschaft Isis. Dresden. 1897, p. 61—64. 

9) C. pe LA Torre, C.R. Congrés Intern. Géol. XI, Stockholm, 1910, p. 1021— 1022. 

0) M. Sancuez—RoiG, Boletin especial de la Secretaria de agricultura, comercio 
y trabajo, Habana, 1920. 

11) C. BurckHarp®, Bolet. Instit. Geologico Mexico, 29, 1912. 


265 


in America. The investigations of Americans have negatived rather 
than substantiated Sugss’s conceptions in some respects. J. W. SPENCER *), 
for instance, came to the conclusion, chiefly after the study of charts 
and morphological speculations in connection with them, that the 
Antilles were not the remains of an old cordillera. This researcher 
maintained that the whole tract of the Caribbean Sea, the Antilles 
and the Gulf of Mexico constituted an ancient continental region, 
which ever since the Miocene had executed the most stupendous vertical 
fluctuations of an amplitude of many thousands of meters. R. T. Hin), 
however, who visited many of the Antilles, is by no means inclined 
to consider most of these islands as other than true oceanic formations 
and refuses to believe that there is any connection between the 
northern Antilles and Barbados-Trinidad, the latter being by him 
assigned to the South-America mainland. In his aversion to the 
assumption of old-sedimentery cores in the Antilles east of Western 
Cuba he even goes the length of questioning the results of Brrev (1.c.) 
who had established the occurrence of old schists in Haiti ou the 
basis of simple petrographic work. 

Neither were the long-continued explorations of T. W. Vaueuan®), 
who has contributed so largely to the knowledge of the geology of 
Central America in modern time, based upon the ideas of Sugss, 
which, as shown above, were of such pregnant significance for 
many a European explorer. 

Particularly the island of Cuba, where since the Spanish-American 
war a number of American explorers have been working, seemed 
to have many features not belonging to the other Antilles. The 
Spanish mining-engineer Sarreratn already had mistaken a group of 
sharply _ folded rocks from the environs of Habana, where fossils 
had never been found for cretaceous sediments *) and the later 
American‘) explorers adhered to this view or contended it only 


1) J. W. Spencer, Geol. Magazine (4), I, 1894, p. 448—451; Bull. Geol. Soc. 
America VI, 1895, p. 103—140; Transactions Canad. Instit., V, 1898, p. 359—368, 
and many other publications. 

*) R. T. Hitt, Bull. Museum. Comp. Zoology, Harvard Coll, 34, 1899, p. 225 
sqq-: Bull. Geol. Soc. America, XVI, 1905, p. 248—988, and many other publications. 

3) T. WayLAND VAUGHAN, Bulletin U.S. National Museum, Washington, 103, 
1919; Contributions to the geology and paleontology of the West Indies, publ. by 
the Carnegie Inst. of Washington, 1919, in which older publicatious are cited in 
extenso. 

4) P. Satreratn, Boletin Mapa geologico de Espafia, VII, 1880. 

5) R. T. Hux, Amer. Journal of Science, (3), 48, 1894, p. 196— 212. Bull. Mus 
Compar. Zoology Harvard Univ. Geol. Series I, 1895, p. 243-288; B. Wixuis, 
Index to the stratigraphy of North America, US. Geol. Survey, Profess. Papers, 
Zale aks Mes 


266 


reservedly'). However, the petrographic habitus of this would-be 
cretaceous formation, made up of white limestones, of soft, white 
marls and of loose caleareous sandstones, is quite different from all 
the cretaceous rocks known from the other Antilles, Central America 
and Northern South-America, sothat Cuba seemed to be isolated 
from the rest in this respect. Another peculiarity of Cuba seemed 
to be that on the whole the tertiary is not very thick and only feebly 
folded: Hitn?) says that the tertiary is merely a thin veneer over- 
lying the older formations sothat its thickness does not excel 1000 
feet, and Hayes-VauGHaN-Seencer have reproduced profiles of the 
island in which everywhere a very feebly folded tertiary formation 
is marked’). If this is correct, Cuba differs very much from the 
other Antilles, for in Haiti‘), Babados as well asin Trinidad ‘) there 
are very thick and intensely folded tertiary deposits, as may be 
expected in a young mountain-range, such as SvEss asserts the 
Antilles to be composed of. 

A two months’ stay in Cuba, in the months of March and August 
of the past year, put me in a position to explain this seeming con- 
tradiction and to detect some striking resemblances between Cuba 
and the other Antilles. ? 

First of all the so-called cretaceous deposits in the environs of 
Habana were explored. They can readily be examined in numerous 
exposures along roads and railway cuts in and near the capital. 
They are composed of white soft, sometimes nodular, fine-grained 
marls; of light-coloured, youngish looking, organogenetic limestones, 
which are seldom very pure, most often however contain some 
voleanic tuff-material; of true submarine tuffs; while sometimes also 
peculiar fine-grained limestone-breccias occur in the formation. In 
numerous spots I found in the limestones and in the submarine 
tuffs micro-organisms, which could be determined in microscopical 
sections. It now appeared that besides a number of Foraminifera, 
insignificant for the age of the formation, and besides: Lithothamnia, : 


1) C. W. Hayes, T. W. VaueHan and A. C. Spencer, Geology of Cuba, 1901 
reprinted in 1918 by the Direccién de Montes y Minas at Habana. 

2) Ro Tbr, Iie: 

8) C. W. Hayes, T. W. VauGHan and A. C. SPENCER, l.c. 

4) L. TripPENHAUER, Peterm. Geogr. Mitteilungen, 1899, p. 25—29, 153—155, 
201—204; 1901, p. 121—127, 169—178, 193—199; 1909, p. 49—57. W. F. 
Jones, Journal of Geology, 26, 1918, p. 728—758. 

5) |. B. Harrison and A. J. Jukes Brown, The geology of Barbados, 1890, 
and other publications. G. WALL and J. Sawkins, Report on the geology of Tri- 
nidad, Memoirs Geol. Survey, London, 1860. 


267 


also small Nummulinae and Orthophragminae occur in various local- 
ities and Nummulinae and Lepidocyclinae in other places. I encount- 
ered in various tuffish limestones between Ardai and Arroyo Naranjo 
small Nummulites and Orthophragminae, while in limes, south-east 
of Regla, to the south of the bay of Habana and to the north of 
Guanabacoa, besides Nummulites also small Lepidocyclinae were 
found, which also occur in the railway-cut, north-east of Palatino 
(the finding-places are marked on the accompanying map).') This 
“Older Habanaformation” is intensely folded, with dominant W—E. 
strike, and rapidly alternating steep dips, so that no positive opinion 
can be formed about the thickness of the whole complex of layers 
with its few well-continuous sections. This thickness however is 
sure to be very considerable. It is evident that this formation, which 
contains Nummulites and Orbitoides, and which, in concurrence 
with Sanreratn (l.¢.) was generally mistaken for cretaceous, is of 
a distinctly more modern type, being nothing else but the well- 
developed and intensely folded eogene, which we recognize with 
the same tectonic and partly also with the same petrographic features 
in so many localities of the Antilles. The occurrence of Orthophrag- 
mina implies that part of this intensely folded formation is decidedly 
eocene. We will endeavour to ascertain whether perhaps subsequent 
parts of the Tertiary are represented in this complex. 

If the fossils, occurring in the ‘Older Habana-formation’’, had 
been found in Europe or Asia, there would be no doubt whatever 
about the occurrence also of oligocene and maybe even of old- 
miocene rocks in this complex, as in Europe as well as in Asia 
Lepidocyclinae are characteristic of the oligocene and the older 
miocene (Stampian to Burdigalian). However, in America Lepidocy- 
clinae have been found also in unmistakably eocene deposits,*) so 
that their occurrence in the vicinity of Habana is in itself no evidence 
at all. Now, the American species in positively eocene rocks (south- 
eastern part of the United States), are all large species, except one 
(L. floridana Cushmann with a diameter of 4—8 mm.). In San 
Bartholomew (L. antillea Cushmann with 5 mm.) and in the zone 
of the Panama-canal (L. Macdonaldi with 5—7 mm.) there occur, 
it is true, some smaller species in rocks, taken to be eocene, but 
the age of these deposits is not so well established as that of the 


1) It is a pity that the names in the map are rather illegible but with the 
aid of a reading-glass it will be possible to recognize most of them. 
4) J. Gusumann, U.S. Geological Survey, Professional Paper, 125D, 1920. 
T. W. VauaHan, Proceedings First Pan Pacific Conference, Honolulu, 1921, 
p- 754—755. 


268 


formations of the South-east of the United States. Now, in the 
Habana rocks, described above, large Lepidocyclinae are absolutely 


lacking; they contain only dwarf-species which — as experience 
in Asia and Europe has taught us — are more or less indicative 


of younger formations, so that part of the “Older Habanaformation”’ 
must very likely still be referred to the Oligocene. And this is not 
all. In the city of Habana and west of it the Older Habanaformation 
is overlain by rocks of quite similar petrographic habitus, but they 
are much less disturbed. These rocks of the ,,Younger Habana- 
formation” (organogenetic limestones, white and yellow marls, sub- 
marine tuffs) form namely a monocline, whose core still exhibits 
steep dips — up to 40° and higher —. The younger portions of th4s 
formation, however, which in its totality is dipping towards the 
sea, are much less steep. In the suburb of Vedado the marls of 
this formation are overlain by coral-limestones which are also dipping 
down towards the sea. The rocks of this “Younger Habanaformation”, 
which are so beautifully exposed in the marlpits of Puentes Grandes 
and of Cienaga and at the Castillo del Principe, are lying uncon- 
formably — as the accompanying map indicates — on the rocks 
of the “Older Habanaformation”’: while the strike of the older rocks 
is K.—W., that of the vounger is about N.E.—N.N.E. The facts, 
however, that in the deeper parts of the younger formation the 
layers are very sharply inclined, and that there is a remarkable petro- 
graphic similarity between the two formations tend to show that 
the stratigraphical gaping between the two formations is only very 
inconsiderable ; nay, in all probability, the uneonformity is only 
“tectonic”, is originated during the folding, and the two formations 
succeed each other most likely without a significant stratigra- 
pbical gap. 

Now, M. Sancunz Roie*) has for several years been collecting fossils 
from the marlpits of Cienaga. It is especially the teeth of Selachii 
that were encountered here. They point to a miocene age, while 
the more southern limestones of Vedado belong even to the Pliocene. 

The foregoing no doubt justifies the conclusion that the rocks of 
the “Older Habana formation” belong partly to the eocene, partly 
to the oligocene, that the tertiary orogenetic movements in this part 
of Cuba began towards the close of the Oligocene, and that they 
continued even in the Pliocene. 

So while in the North the layers of the “Older Habanaformation” 
are overlain unconformably by miopliocene rocks, which have still 


1) M. SancHez RorG, Boletin de Minas, Habana, N°. 6, 1920. 


269 


co-operated in the crustal movements, in the South near Arroyo 
Narranjo limestones are overlying the “Older Habanaformation”, 
which are perfectly horizontal and can be traced southward as far 
as Guira, invariably in horizontal position. Near Arroyo Narranjo 
these limestones, which in their habitus differ greatly from the 
rocks of the ‘Older Habanaformation”’, are coastal limestones; 
farther to the south also Globigerina limestones occur. As a matter 
of fact these limestones, which have had no share in the latest 
orogenetic movements, must be of more recent date than the mio- 
pliocene rocks of the “Younger Habanaformation” and belong con- 
sequently to the Youngest Pliocene or Pleistocene. These limestones, 
which the Geological survey-map of North-America’) still. marks as 
Old Tertiary, have lent support to the opinion that the Cuban 
Tertiary is only feebly folded, and that the Tertiary constitutes only 
a thin varnish overlying the older formations. 

This does away with the seeming contrasts between Cuba and 
the other Antilles and replaces the island in the homogeneous range 
of the Antillean Cordillera. 

In an excursion to San Diego de los Baiios, about 100 k.m. to 
the west of the capital I encountered also here a well-developed 
and intensely folded eogene formation; to the North of this small 
town mesozoic limestones emerge, but farther to the south intensely 
folded rocks (strike E.-W.) are exposed everywhere — especially 
submarine tuffs — containing Lithothamnia, Nummulites and Ortho- 
phragminae. Globigerina marls also occur. 

The Petrographic composition of the Cuban Tertiary is interesting 
also in other respects. First of all, in the Older as well as in the 
Younger Habanaformation limestones occur that, being examined 
microscopically, appear to contain much young volcanic material, 
nay in many cases, even change into true calcite-poor, submarine 
tuffs. Sharp angular splinters of plagioclase and quartz are numerous. 
Likewise numerous grains present themselves, of a substance con- 
taining plagioclase microlites, granules of ore and glass, which are 
to be considered as ground-mass fragments of an andesitic or dacitic 
rock. Similar eogene, submarine tuffs were also recognized in the 
Tertiary of San Diego. Much voleanie material also occurs in mio- 
pliocene deposits of a shallow sea (coralligene limestones, marls, 
calcareous sandstones and finely granular conglomerates), which are 
excellently exposed in the Yumuri cleft near Matanzas, about 75 k.m. 
east of Habana. On the contrary voleanic material seems to be 
lacking entirely in the very young, horizontally disposed limestones 
yy B. Wits, Le. 


270 


found near Arroyo Naranjo, Rincon, San Antonio de los Banos and 
Guira. In one of the younger portions of the Yumuri cleft-profile 
feldspars were so numerous that they could readily be examined in 
the pulverized rock. All the splinters that were examined, had a 
higher refractive index than canada balsam, so that there is a 
complete lack of orthoclase and albite. Among 20 splinters examined 
13 bad a higher, 7 an equal or a lower refractive index than 
eugenol (1.546), so the latter belong to oligoclase. Nearly all the 
splinters have a lower refractive index than nitrobenzol (1,556), so 
that among the larger feldspar splinters, which are of course 
fragments of phenocrysts from the dacitic-andesitic rocks, from which 
also the ground-mass originates, no plagioclases occur that are more 
basie than andesine’). The effusive rocks supplying the material for 
submarine tuffs, must then have been a highly acid, potassium- 
poor dacite i.e., a rock in all points of the type of the “Pacific Rock”. 

It should be observed that the fragments of the ground-mass 
occurring in the tuffs, very often have a diameter of 1 mm. It is 
not out of the bounds of possibility of course, that similar volcanic 
material could have reached Cuba during an eruption of rather 
remote voleanoes, if at the time of the eruption a violent storm had 
been blowing in the direction of the island. The coarseness of the 
fragments, however, together with the very high frequency of 
voleanic material in formations extending from the eocene into the 
pliocene in localities nearly 200 k.m. apart, indicate that this 
material has not ‘come over’ under ‘peculiar’ circumstances from 
far-away volcanic centra. These submarine voleanic tuffs that are 
so widely diffused both stratigraphically and geographically, must 
be regarded as evidence that in the Tertiary the volcanic activity 
in the Antillean region extended over a much larger area than at 
present and that it did not settle down before the close of the 
Tertiary. This fact also tends to strengthen our view that the Antilles 
are geologically homogeneous. 

It is likewise deserving of note, that no remains whatever are to 
be found of the volcanoes that must have existed as late as the 
latter half of the Tertiary in the neighbourhood of Cuba. This 
proves that already since the beginning of the Tertiary Cuba must 
have been subject to violent disturbances, where denudation destroyed 
rapidly what had been built up by voleanie and orogenetic processes. 


1) The refractive indices of the fluids used in the Utrecht geological institute 
for the determination of the refractive indices of minerals, have been verified only 
a short time ago by Prof. ScHoorL for which we tender our thanks. 


271 


Presently we shall see that other facts also corroborate this hypothesis. 

In the vicinity of Habana a deeply weathered serpentine-massif 
(see sketchmap) has long (SatTerain |. c. and others) been known. 
In two localities — south of Guanabacoa and due south of the bay of 
Habana — quartzamphibole diorites are found as a dyke. These 
moderately acidic plagioclase rocks forcibly reminded me of the 
granular crystalline rocks of the ‘Pacific ty pe’, described by Hécsom (Ie.) 
and derived from the Virgin Isles. The felspars of this quartz- 
amphibolediorite all had a refractive index higher than canada 
balsam, but the refractive index of most of them was lower than 
that of quartz, to which they often are contiguous in the micro- 
scopical sections. Consequently they belong to the acid portions of 
the plagioclase series. [ndeed the fact that this rock is poor in 
potassium and comparatively rich in silicie acid (much quartz and 
many acidic plagioclases) reminds us forcibly of many ‘‘Andes-rocks”’. 
Also by the occurrence of granular rocks of this type Cuba is united 
to the American continent on the one side and on the other to the 
Virgin Isles. 

When perusing the literature concerning the Antilles we are 
impressed with an other incongruity between Cuba and the other 
Antilles. Already long ago young Radiolaria-bearing deposits became 
known in Barbados (Harrison and Jukes Brown, |. ¢.) which many 
geologists regard as true deepsea-deposits. R. T. Hint also described 
tertiary Radiolaria-deposits in the east of Cuba (Baracoa). However, 
whereas in Barbados the Radiolaria deposits overlie unconformably 
the older tertiary — which developed there as a terrigenic deposit — 
and have only been subject there to faulting and not to folding, 
the Radiolaria deposits of Baracoa have a steep dip, so that there 
seemed to exist a stratigraphical incongruity between these deposits 
in the two islands. In the neighbourhood of Habana I encountered 
Radiolaria-bearing rocks in two levels ofthe Tertiary. In the first 
place white marls in the “Older Habanaformation” near Cerro, 
with a dip of 75° southward. They are entirely filled up with 
Radiolaria that belong for the major part to the Spumellaria, for 
a small part however also to the Nasselaria (fig. 1). Secondly, in 
the most recent part of the ‘Younger Habanaformation’’, i. a. in 
the marlpits of La Cienaga, white Globigerina marls occur which 
contain a not inconsiderable amount of Radiolaria. Now it is very 
well possible that the Radiolaria-marls of Cerro are the equivalent 
of those of Baracoa in Hast-Cuba, whereas the Radiolaria-bearing 
Globigerina marls of La Cienaga are stratigraphically more like the 
deposits in Barbados. Also the contrast which apparently exists in 


272 


this respect between Cuba and some of the other Antilles finds an 
explanation in the above. 

Indications of the homogeneity of the row of Antilles can also 
be found in the older formations of Cuba. As stated previously, of 
late years Malm-ammonites have been found near Vinales, in the 
most western part of Cuba. These Upper-jurassie layers, which dip 
away to the North at a rather small gradient, are overlain by thick, 
old-looking grey limestones with intermediate layers of sandstones, 
which, therefore, are probably to be referred to the Cretaceous 
system. In one place I found in these limestones small nests of red 
chert; under the microscope this red chert appeared to be a true 
Radiolarite, very much like the Radiolarites so widely diffused in 
the mesozoic rocks of the southern Molucean-cordillere (fig. 2). The 
geological institute at Utrecht possesses a number of rocks from the 
islands of Curacao, Bonaire and Aruba, collected by Dr. I. Bo.pinen. 
Among the rocks from Bonaire and Curacao it was not difficult to 
recognize Radiolarites — probably mesozoic — bearing close resem- 
blance to those from Cuba.’) This is not all. In the coral-limestones 
of the Yumuri-cleft near Matanzas coarse clastic material was found; 
boulders to a maximum of 7 mm. in diameter. Four of them were 
ground, of which two appeared to be red radiolarites like those 
found to the north of Vinales, while in our days mesozoic sediments 
are lacking in this part of the island. 

It is evident, therefore, that such a peculiar sediment as the mesozoic, 
red radiolarite is found at the extremities of the Antillean region: 
in the most western part of Cuba and in Bonaire and Curacao. 
This, no doubt, warrants the assumption that the Antillean region 
is One continuous whole, parts of which, in spite of their different 
appearance, have many features in common, that point to an 
historical homogeneity. 

From the occurrence of much voleanic material in the whole 
tertiary of Cuba, in the neighbourhood of which no volcanoes exist 
any more, we may conclude that the island must have been subject 
to great geological disturbances in recent times. A similar conclusion 
may be deduced from the great abundance of boulders of cretaceous 
Radiolarites in the miopliocene of the Yumurt-cleft, as these boulders 


1) K. Martin, Bericht iiber eine Reise nach Niederl. West Indien, Il, 1888, 
p- 28 and 73 and J.H.Ktoos, Samml. Geol. Reichs-Museums, Leiden II, 1, 1887, 
already demonstrated the occurrence of Radiolaria-bearing rocks in Curagao and 
Bonaire. From their descriptions it is not evident, however, that we have to do 
here with typical Radiolarites, which at that time did not receive so much 
attention from geologists as nowadays. 


273 


point to a powerful post-eocretaceous mountain-building by whieh 
the deep-seated Radiolaria-deposits were uplifted beyond the sea- 
level, while in the Tertiary the mountains were entirely denuded 
again. 

In the foregoing Radiolaria-bearing deposits have been described 
from three levels of the series of sediments of Cuba: a fourth level 
can still be added. Between Bacuranao and the boring-field which 
is located to the north of this village, green sediments were observed 
in the centre of the serpentine-area. These sediments are distinctly 
seen to dip away below the serpentine. Under the microscope they 
appeared to be in part voleanic tuffs, in part remarkable radiola- 
rites, which consist chiefly of skeletons of Radiolaria, but also 
contain spiculae of sponges, while the silicic acid of the Radio- 
laria as well as of the sponges spiculae is still perfectly amorphous 
(fig. 3). These siliceous sediments are closely connected with the 
voleanic tuffs; not only do the Radiolaria-layers and the tuffs possess 
equal dip and equal strike, but sometimes the siliceous sedi- 
ments contain splinters of plagioclase, and in one of the micro- 
scopical sections the tuff even passes into the siliceous sediment. 
These Radiolarites of Bacuranao certainly belong to an older level 
than the tertiary Radiolarites, as the former dip away. below the 
serpentine, whereas the whole tertiary is more recent than the 
serpentine, whose water-worn fragments are found here and there 
in the tertiary limestones and calcareous sandstones. They belong 
moreover to another level than the red Radiolarites of Viiales and 
Matanzas, for the thick limestones bearing the red Radiolarites of 
Vinales are not found near Bacuranao. The siliceous sediments are 
closely related to the Cuban serpentines. 

Now it is very remarkable that in Cuba such extreme deposits 
as Radiolarites appear in four different levels. Even when not 
assuming that Radiolarites are true deepsea deposits, we must be 
convinced that the formation of these calcium-free or caleium-poor 
siliceous sediments requires conditions that do not exist in the shallow 
epi-continental seas. At all events the occurrence of these deposits 
in at least four levels of the island of Cuba justifies the conclusion, 
that the area in which the island is now situated, was in the latter 
half of the Mesozoicum an extremely restless region, where now 
deposits of a shallow epicontinental sea (sandstones in the Chalk, 
Nummulites and Orbitoide-bearing limestones in the Tertiary), then 
again such peculiar sediments as Radiolavites') could be formed. 


1) One more fact may be adduced to confirm the conception that at least one 
level of the Radiolaria-bearing deposits in Cuba is formed, if not in a true deep- 


274 


There are, indeed, two more arguments for the conclusion that 
Cuba has ever been a very inconstant region, at least since the 
Tertiary. 

In the outset we reminded the reader that already Surss, WicHMANN 
and Martin had pointed out the analogy between the Antilles and 
the southern Moluccas, which analogy is brought out in a similar 
arrangement of the tectonic elements. Two points have been discussed 
above to emphasize this analogy. In the first place the occurrence 
of Red Radiolarites, so very typical of the Mesozoicum of the 
Moluceas. in the two extremities of the Antilles. In the second 
place the conception that in the latter geological periods the Antillean 
region was so extremely restless. It is known, indeed also of the 
southern Moluceas, that their region was very changeable, and was 
characterized by great instability in the relations of land and sea: 
also there the formation and the denudation of mountains took place 
in such rapid succession, that it is difficult to disentangle the develop- 
ment of the geological history. We may add even one more detail 
in comparing the instability of the Antillean region with that of 
the southern Moluceas. In the Antilles it struck us that in one and 
the same island Radiolaria-deposits occur at least in four different 
levels. Why, also of the island of Rotti, near Timor, Brouwer has 
described’) Radiolaria-bearing deposits in three totally different levels: 
Upper Trias, Malm and Tertiary. 

Utrecht, May 1922. 


sea, anyhow in a sea of considerable depth. In the white marls of La Cienaga, 
where many Globigerina and also numerous Radiolaria occur Sanchez-Roig (l.c.) 
has found numerous teeth of Selachii. A large number of these teeth (though by 
far not all) display the peculiarity that only the enamel of the teeth is left, while 
the dentin has completely disappeared. This state of preservation is exclusively 
characteristic of Selachii-teeth that are encountered in the deepest sea and in 
deepsea deposits. 

Cf. MoLenaraarr and Breaurort, Proceedings XXIX, 1921, p. 677—692. 

') H. A. Brouwer, De Nederlandsche Timor Expeditie, III, 1921. Geologische 
onderzoekingen op het eiland Rotti. 


DESCRIPTION OF THE PLATES. 


Fig. 1. White Radiolariamarl. Older Habanaformation. & 26. 

Fig. 2. Red Radiolarite. Viiales. X 26. 

Fig. 3. Silicious rock with Radiolaria and Sponge-spiculae. Bacuranao. x 26. 
Fig. 4. Geological Sketchmap and transverse profile of the vicinity of Habana. 


—,—.— Railways: 
ABC—CD Line of Profile. 
S. Serpentine. 

D. Quartzhornblendediorite. 
A. Petroleum Rigs. 


L. RUTTEN: “Cuba, The Antilles and the Southern Moluccas’’. 


Fig. 4. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Bio-chemistry. — “Changes in Milk due to Sterile Inflammation 
of the Udder.” By Prof. B. Stontema and J. KE. van per Zanpe. 
(Communicated by Prof. C. Eykman.) 


(Communicated at the meeting of May 27, 1922). 


The examination of a number of samples of abnormal milk from 
cows suffering from clinically observable affections of the udder, 
as well as from cows in which clinically no anomalies of the 
udder were noticeable, impressed us in 1921 with the idea that 
too great an importance is ascribed to streptococci as causative 
agents of the secretion of abnormal milk. We found for instance 
that in very abnormal milk streptococci are often absent.') We, 
therefore, decided to go further into this subject and produced 
sterile inflammation of one of the quarters (R. F.) of the udder of 
a milch-cow in full lactation, with the aid of a suitable injection. 
On the suggestion of Prof. Paimans a solution was administered of 
of silver-nitrate of 0,2 °/,.*) 

In the same cow a sterile abscess had previously been developed 
through injection of oil of turpentine in the region of the neck with 
a view to ascertain whether such a sterile inflammation exerted 
any influence on the secretion of milk. We were induced to do so, 
because in a previous investigation in our laboratory anomalies had 
been found in the milk yielded by animals which were affected by 
inflammation of quite other parts of the body than the udder. 

The results obtained after the injection of oil of turpentine need 
not take us long. Although a considerable abscess had developed, 
the composition of the milk did not undergo a notable change, 
neither during the development, nor after the abscess had become 
mature. 

Once the sediment of the milk from one of the quarters had 
increased a little, of which the abscess may not have been the 


‘) Our report pertinent to the matter in question appeared in Tijdschrift voor 
Vergelijkende Geneeskunde enz. Band 7 1922. 

*) We were in a position to prosecute this inquiry thanks to the aid of Prof. 
W. J. Parmans and the Conservator for Obstetrics, Mr. J. A. J. M. Krrow, whose 
assistance we acknowledge with gratitude. 


276 


cause. It would seem, therefore, that a sterile inflammation does 
not affect the secretion of milk in the same way as a bacterial in- 
flammation has in our earlier researches repeatedly proved to do; 
this result could be expected. 

The effect of the sterile inflammation of the udder with silver- 
nitrate solution was quite different. The very next day (9 March) 
the composition of the milk had changed very much, as was also 
the case on the following days, when the milk presented also a 
very abnormal aspect. 

Gradually composition and aspect improved ; however, this quarter 
became choked before the milk was quite normal; at all events not 
a trace of milk could be drawn on March 19 and following days. 
The examination of the milk-samples gave the results tabulated on the 
following page. For the sake of comparison we have also tabulated the 
figures of some abnormal milk-samples with (N°. 164 and 142) and 
without (N°. 181 and 267) streptococci, which samples were examined 
in 1921. For the same reason we included the figures obtained from 
the same quarter (R. F.) of the injected cow before this treatment 
(N°. 343 and 337) and from other quarters (N°. 385 and 381) after 
the injection. 

The table shows that the milk from the quarter injected with 
silver-nitrate possessed, — with the exception of the presence of 
streptococci, — all the properties of milk from animals, suffering 
in a high degree from udder-affections e.g. streptococci mastitis). 
Acidity, p,, sediment after centrifugation in Trommsdorff-tubes, 
leucocytes, chlorin-, and lactose-content, were all changed in the 
same measure,') as were also the total protein-content and the 
calcium-content. 

Furthermore the content of total, combined-, and free carbonic 
acid appeared to have increased, just as in milk from cows with 
diseased udder. This anomaly and its connection with the bydrogen- 
ions concentration of milk has been pointed out in 1919 by L. L. 
vAN SLJKE and J. C. Baker’). 

Lastly, the tryptophane-content appeared to be considerably in- 
creased. In 1921 we found this content in abnormal milk (derived 
from diseased udders), and in colostrum to be very high. This is no 
doubt due to the occurrence in these kinds of milk of much protein, 
which is identie with, or related to the globulins of bloodserum, 
just as the other anomalies of the milk from cows with diseased 


1) Milk containing streptococeci has sometimes a high degree of acidity. 
2) Journ. Biol. Ghem. 40. 335 (1919). 


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Proceedings Royal Acad. Amsterdam. Vol. XXV. 


278 


udders are connected with the transit of bloodplasma-components 
in abnormal milk. While 100 ¢.c. normal milk — after removal 
of casein and fat with the aid of potassium-alum contain according 
to our investigations about 14—20 mers. of tryptophane, as much 
as 348 mgrs. occurred in the milk-samples after the injection of 
silvernitrate, that is about twenty times more. 

The determination of the tryptophane-content, easily executed by 
the colorimetrical method of von Firta and Noset'), is no doubt 
one of the most accurate methods for examining the normality 
of milk. 

The foregoing experiments tend to show that the anomalies 
characteristic of streptococci-containing milk, arise also from sterile 
inflammation of the udder-tissue, so that streptococci need not always 
be essential to the occurrence of similar anomalies. The question 
whether, in the case of streptococci-mastitis, these bacteria are very 
often only of secondary importance can of course not be answered 
on the basis of this investigation. 

From the Chemical Laboratory of the Veterinary 
University of Utrecht. 


) Biochem. Zts. 109. 103. (1920). 


Microbiology. — “On Bacillus polymyaa’'). By Prof. M. W. 
Beerinck and L. E. pen Dooren pr Jona. 


(Communicated at the meeting of September 30, 1922). 


If the species-conception is taken in a not too limited sense, the 
closely related, but not identic forms mentioned in Note 1, may be 
said to comprise the only known aérobic spore-forming bacterium- 
species, which causes fermentation in a sugar-containing medium. 
We call it Bacillus polymyaa. 

It is rather generally spread in fertile soils; its properties are 
very characteristic and give rise to interesting experiments. The 
production of aceton first observed by ScHARpINGER, has in the later 
years drawn attention on this microbe, but the quantity formed is 
small and from malt or potatoes it does not amount to 1°/, of the 
weight. But the conditions for its formation are not yet well-known 
and might perhaps be greatly improved as to the quantity. Alcohol 
is also generated and to a somewhat greater amount than aceton. 
Besides, a little acetic- and formic acid seem to be produced. Par- 
ticularly the secretion of the enzyme pectinase and of much slime 
by the chief variety is of interest. 


1) The literature of this Bacterium and its nearest relations is to be found under: 
Clostridium polymyxa Prazmowski, Granulobacter polymyxa Beiseriwncx, Bacillus 
macerans Scuarpincer and Bacillus asterosporus A. Meyer. — A. PRazmowski, Ent- 
wickelung und Fermentwirkung einiger Bacterién. Dissert. Leipzig 1880, p. 37. — 
Tu. Gruper, Identifizierung von Clostridium Polymyxa Prazmowskl, Centralbl. f. 
Bakteriol. 2te Abt. Bd. 14, 1905, pag. 353.-— F. Scuarpincer, Bacillus macerans, 
Acetonbildender Rottebacillus, Centralbl. f. Bakt. 2te Abt. Bd. 14, 1905, pag. 772. 
Zur Biochemie von 5b. macerans. Centralbl. f. Bakt. 2te Abt. Bd. 19, 1907, p. 161. 
Kristallisierte Polysaccharide aus Starke durch Mikrobien. Centralbl. f. Bakter. 2te 
Abt. Bd. 22, 1909, p. 98 and Bd. 29, 1911, p. 189. — A. Mewser und G. 
Brepemann, Variation und Stickstoffbindung durch Bacillus asterosporus. Centralbl. 
f. Bakteriol. 2te Abt. Bd. 22, 1909, p. 44. 

The name asterosporus is derived from 9 or 10 rims on the exosporium of 
the oblong spores, which make the transversal section star-like. By abundant 
feeding, as on wort-gelatin, many rodlets change into narrow clostridia con- 
taining somewhat granulose, colored blue by jodine; so the species may also be 
called Granulobacter polymyxa. 

18* 


280 


Accumulation and occurrence. 


Long ago the following experiment for the accumulation of this 
species was described *). 

Coarsely ground rye with some chalk and inoculated with fertile 
garden soil is mixed with water in a deep beaker to a thick solid 
paste, boiled during some seconds to kill the non-spore-formers and 
cultivated at 25° to 30° C. As the spores of B. polymyxa soon die 
at boiling, the heating must last but a short time. After a few days 
the surface is covered with a coherent film of B. mesentericus *) and 
other closely related species, while in the depth a butyrie-acid fer- 
mentation takes place, usually simultaneously with butylie-alcohol- 
and polymyxa fermentation. 

It is clear that this accumulation reposes essentially on a tempo- 
rary anaérobiosis of B. polymyxva, which can also grow aérobie and 
so behaves like the alcohol yeast and the Aérobacter-Colgroup among 
the bacteria. The rye produces the sugar causing the fermentation, 
i.e. the source of energy, which makes the anaérobiosis possible so 
* is still sufficiently present, albeit 
chemically non-demonstrable, whereas the want of ‘oxidation 


long as the “excitation oxygen’ 


oxygen’, which is required for aérobiosis in much larger quantity 
as source of energy, is temporarily excluded. Pasrrur’s statement : 
“la fermentation est la vie sans air” is evidently applicable to B. 
polymyaa. 

By sowing out the fermenting matter from the depth on wort- 
agar, ordinarily already after few days the polymyxa colonies become 
visible as lumps of slime, together with the unavoidable flat spread- 
ing colonies of B. mesentericus. 

This method can only produce those varieties of B. polymyxa 
which are able to resist a relatively high concentration of the food. 
Another accumulation method by which also forms adapted to a 
lower concentration of food are obtained is based on the aérobiosis 
of our bacterium. 

After the observation had been made that flasks of boiled wort, not 
sufficiently sterilised, were not seldom spoiled at the low temperature 
of 15° C. by the development of B. megathertum and never by B. 
mesentericus, whose germs were certainly also present, the question 


1) M. W. Beiserinecx. De butylalcoholgisting en het butylferment. Academy of Sciences. 
Amsterdam 1893. 

*) This film may be colourless, brown, red, and even jet black according to the 
accidentally present varielies of B. mesentericus. The black form is rare and 
sometimes obtained by the “mesentericus experiment’ with unwashed currants 
(boiling with chalk, cultivating at aération at 30° to 40° C.). 


281 


arose: which are the aérobie spore-forming bacteria, which can 
develop at temperatures of 15° C. or lower and under favorable 
feeding conditions? We knew already that the obtaining of B. 
megatheriwm might give an answer to the question, for example in 
case the spores of this species were only present with those of 
BS. mesentericus, but it seemed possible that free competition with 
the soil bacteria would exclude 2. megatherium and that some other 
species could appear. The chief aim of the experiment was to 
exclude B. mesentericus, the common hay bacterium, which produces 
substances very noxious to other species, and this is to be reached 
by the low temperature, as the minimum for the growth of this 
species is at about 20° C. The simultaneous development of B. 
megatheritum is of less importance as it is innocuous to other kinds. 
Of course we had to reckon with the butyric-acid and butylic fer- 
mentations, which may very well occur at 15° C, but strong aéra- 
tion prevents them efficiently. 

Although we could expect that the one or more species that were 
to develop under the chosen conditions would possess a higher 
temperature optimum than that used by us, we had not to fear a 
failure if only we cultivated above their minimum. 

Knowing that the spores of some spore-formers, for example those 
of the butylic ferments, and thus perhaps, too, those of the species 
we sought for, could not or hardly resist boiling, the heating of 
the culture liquid containing the inoculation material and wanted 
for killing the non-spore forming species, was not continued much 
above 85° -or 90° C. and only for a few seconds. We used flasks 
half filled with about 30 eM’ liquid, and in order not to miss 
somewhat rarer species, we inoculated with so much soil that on 
the bottom a layer of about 1 cM precipitated. This soil had 
previously been well-divided and freed from coarse particles. In 
such a thick layer a beginning of anaérobiosis is possible, but by 
shaking, butyric-acid or butylic fermentation may easily be stopped. 

For. food we used at first malt-wort, diluted to 2° to 5° BaLuine, 
later broth-bouillon with 2°/, to 5°/, cane sugar, or glucose. Addition 
of chalk is not absolutely wanted for the success of the experiment 
but its presence proved favorable. 

After we had ascertained with pure cultures of B. polymyaa that 
ammonium salts, nitrates and asparagine are very good sources of 
nitrogen, we also accumulated with sugars and ammonium. sul- 
phate, in a solution of tapwater 100, 2 to 5°/, glucose or cane 
sugar, 0,05°/, (NH,),SO,, and 0,02°/, K, HPO, with some chalk. 
The execution of the experiment is as above, but afier pasteurising, 


282 


the butyric-acid fermentation must be more completely excluded 
than when using broth-bouillon or malt-wort. For although the latter 
liquids contain an excellent nitrogen food for B. polymyxa, they are 
of Jess value for the butyric-acid ferments, for which the ammonium 
salts are preferable. Hence, in this case it is advisable to use a large 
ErRLENMEWERflask, as the great volume of soil which sinks to the 
bottom as inoculation material, can then be better aérated, by which 
butyric fermentation is prevented. 

Although the growth is slow at the low temperature the liquid 
becomes distinctly turbid and in most cases this is accompanied 
with fermentation. This fermentation especially awakened our atten- 
tion as we had expected an accumulation of B. megatherium, which 
causes no fermentation at all. 

As the Coli- and Aérogenesfermentations had been prevented by 
the previous heating, the butyric-acid and butylic fermentations by 
the aération, we now expected that the fermentation of B. polymywxa 
was obtained, and this was confirmed by the pure culture. The 
fermentation which is chiefly an alcoholic one, proves that our bacte- 
rium belongs to the facultative (temporary) anaérobes, and the exa- 
mination of the gas showed that it is almost pure carbonic acid. 

One of the most notable qualities of B. polyinyxa is its secretion 
of pectinase, i.e. the enzyme by which some microbes dissolve the 
central lamellum of plant tissues, thereby disintegrating them into cells. 
Hence, B. polymyxa like B. mesentericus may under certain cireum- 
stances play a part in the retting of flax, although the real agent in 
this case is the anaérobie B. pectinovorum. 

Beans, peas and other plant seeds, left to spontaneous corruption, 
may change into rich cultures of . polymywa, the cell-walls of 
cotyledons and of endosperm being easily attacked by pectinase, 
whereby the interior of the seeds is changed to a pulpous mass ’). 
For the preparation of a pure culture this method is less recom- 
mendable than the two foregoing accumulations, on account of the 
numerous hay bacteria which thereby simultaneously develop; it is, 
however, a good way to get an initial material for the said accu- 
mulations themselves. 

It seems to us that the generality of B. polymy«a in our surroun- 
dings and particularly in the soil should be explained by its pectinase 
secretion, which must give this species, in combination with its little 
want of air, a great advantage over the other saprophytes. 


) The enzyme seminase, which changes the endosperm of the Leguminosae 
(Indigofera, Ceratonia) into mannose, is perhaps identie with the pectinas of 
B. polymyxa. 


283 


The very common presence of Bb. polymyxa in the bark of the 
nodules of the Leguminosae is certainly also a direct consequence of 
its pectinase production. Its presence there is of so general occurrence, 
that it reminds more of symbiosis than of saprophytism. In the 
bacteroidal tissue B. polymyxa is however completely absent. 


Properties of the colonies. 


The colonies on agar as well as those on gelatin are characteristic. 
On malt-wort gelatin they resemble at first thin, watery, sideways 
quickly extending, slowly  liquefying layers, which by and_ by 
become deeper and cloudy by their strong growth. At length the 
gelatin is completely liquefied and then these cultures resemble those 
of common hay bacteria. On malt-wort agar there is a profuse produc- 
tion of slime, whence very distinct voluminous and wrinkled 
colonies appear. The slime attracts part of the pigment from the 
wort-agar thereby becoming brown-coloured, which gives a character- 
istic appearance to the colonies. 

On glucose-kalium-pbosphate-ammonium-phosphate-agar they be- 
come glass-like transparent, somewhat resembling glass globules, so 
peculiar that at estimating the number of germs in soil samples, they 
may directly be recognised and counted. Silica plates, saturated with 
food, also produce such drop-iike colonies from soil. Some varieties form 
much less slime than others and this slime is either tough or soft. 

Microscopically those with soft slime consist of much shorter 
rodlets. Hence, one is at first disposed to think of different species, 
but further research shows the similarity, which is the more con- 
vineing, when beside the natural varieties, the mutation phenomena 
in the pure cultures are studied. On cane-sugar-asparagine agar 
many colonies, at first quite homogeneous and soft, when getting 
older produce small, rather solid, transparent, secundary colonies 
which, after separation from their surrounding (which is not easy) 
prove to be constant. On malt-wort agar the variety with tough 
slime, when growing older produces extensive, flat secundary colo- 
nies, showing a hereditary loss of the factors for slime formation. 

In liquid nutritive media the form resistent to high concentrations 
of the food gives remarkable cultures. 

In a malt-wort of 10° Bauiine at 30° they consist of excessively 
voluminous slime masses, forming after one or two weeks a thick, 
coherent, floating film, inflated by carbonic acid, whilst no hydrogen 
is detectable. Only in the anaérobie butylic fermentation something 
of the like may be observed but then much hydrogen is present. 


284 


Even the most slimy Aérobacter torms produce quite different sub- 
merged cultures equally dispersed through the solution. 

The vigorously fermenting slime varieties of L. polymyxa produce 
aceton, probably after the formula 


C,H,,0, + 20, = C,H,0 + 3C0, + 3H,0. 


To the products of the anaérobie fermentation belong in parti- 
cular aethyl aleohol, with traces of acetic acid and formie acid 
beside some other products, such as butylic glycol, in small quantities. 

The less slimy varieties of B. polymyxa can only live in food of 
lower concentration and spread through the solution as Bact. aérogenes. 
Also in other respects there is similarity between Lact. aérogenes and 
B. polymyaa, so that there is cause to conclude to a real relationship. 
Still there is a great difference in so far as aérogenes can assimilate 
many organic salts, a power quite absent in B. polymyxa. 


Nutrition. 


For the investigation of the substances which can be assimilated 
by B. polymyaxa, the auxanographic method is very convenient, 
particularly in relation to the carbohydrates, B. polymyra being a 
real “sugar bacterium’, which produces much cell-wall matter, 
which makes the auxanograms very distinet. In judging the latter 
it should be kept in view that, beside pectinase, B. polymyaa 
produces diastase, invertase and emulsine. In presence of sugar 
various nitrogen compounds are assimilable, of which, however, 
only nitrogen is taken up. We preferently used peptone, asparagine 
ureum, ammonium sulphate and saltpeter. Urease is not secreted ; 
saltpeter is reduced to nitrile, not to nitrogen. 

As in absence of sugar the carbon cannot be withdrawn from 
nitrogen compounds, such as peptone and asparagine, the growth, 
even on broth-bouillon-agar is but slight and is a eriterion for the 
quantity of sugar present. Hence, if on this medinm £. polymyzxa 
is densely sown, only small, hardly visible colonies grow, consisting, 
however, of bacteria with abundant protoplasm and commonly 
motile. If on such a culture an assimilable carbohydrate is locally 
distributed, vigorous growth ensues, chiefly reposing on slime for- 
mation and a distinct auxanogram results, demarcated by the limit 
of diffusion of the substance. It is in faet the presence of a small 
amount of complete food at the starting of the experiment, together 
with excess of by themselves unassimilable nitrogen compounds, 
which enables the germs to change into small colonies, which 


j 


285 


renders the further growth after addition of the carbohydrate very 
clear. 

Most sugars and polyalcohols are readily assimilated by B. poly- 
myxa. This we have ascertained for arabinose, glucose, levulose, 
‘mannose, galactose, cane-sugar, maltose, lactose, melibiose, raffinose, 
rhamnose, glycerin and mannite. On the other band sorbite, dulcite, 
erythrite and quercite are not attacked. It is very notable that we 
did not find any organic salt assimilable by this organism. 

The “sugar bacteria’, to which B. polymyva belongs, produce from 
carbohydrates much more visible cell-wall substance than protoplasm, 
if the carbohydrates exceed the nitrogen food and vice versa. 

Hence, B. polymyxwa may be found, as was observed above, in two 
microscopically greatly different conditions. At insufficient feeding with 
carbohydrates, for example on broth agar, it grows as highly motile 
rodlets, without slime wall; at copious feeding with carbohydrates, 
as immotile rodlets with a thick slime wall‘). This circumstance 
leads to the following experiment, only adapted to the variety of 
B. polymyxa which produces voluminous slime and grows strongly 
on malt-wort. 

The bacterium densely sown on cane-sugar-kaliumphosphate-agar, 
containing but few nitrogen compounds, may form fairly large 
colonies consisting, however, almost entirely of the strongly swollen 
walls of the cells. By addition to the said medium of a few drops 
of complete food, for example a little broth or malt-wort, con- 
taining an excess of sugar, the slime walls grow surprisingly so 
that the plate covers with a relatively thick slime coat. This slime 
is built up of the sugars by one or more synthetically acting 
enzymes, that might be named “cyteses’” and should be considered 
as the genes or factors of the cell-walls. 

This slime has the remarkable property of being able to become 
itself a source of carbon food, but only at the moment when all 
the cane sugar and all the assimilable nitrogen compounds have been 
used. If at this time some such nitrogen compound as ammonium- 
sulphate or asparagin are brought on the slime coat of the plate, the 
bacteria begin anew to grow and produce new protoplasm from their 
own cell-walls. This leads to the peculiar consequence, that an aux- 
anogram is produced sinking deep into the layer of slime. For, by the 
growth the bulk of the bacteriais diminished, because the walls, which 
chiefly consisted of water and ‘were very voluminous, disappear 
and are replaced by living protoplasm. So the appearance of the auxa- 


1) Medici give to the cell-wall of bacteria the singular name of “capsule”. 


- 


286 


nograms is quite changed when compared with the original state, 
for by their intense increase the opaque bacteria produce an also 
Opaque auxanogram, whilst the original slime was transparent like 
glass. This proves that, in this case at least, the biological function 
of the slime is that of a reserve food. 

In this experiment cane sugar was the food for the slime pro- 
duction; as hereby inversion takes place, glucose and levulose are 
probably the building materials of the slime; that these sugars are 
assimilated was stated above, and that glucose may also serve for 
the described experiment we ascertained particularly. 

The other sugars have not yet been extensively examined from 
this point of view, but it seems that all give the same result. This 
leads to the conclusion that probably no more than two or three 
factors or genes (endoenzymes) are active in the production of the 
cell-wall. The problem is evidently of theoretic interest and deserves 
nearer research. 

The wall-substance, which certainly belongs to the cellulose group 
and therefore may be called cellulan, must have a high power of 
attraction for water, for else its surprising volume cannot be explained. 
Nevertheless its molecules cannot be very small as they cannot diffuse 
at all in water. It is not colored by jodine, nor is it attacked by 
diastase. But as B. polymyxa may use it as a food-substance, this 
species evidently can excrete an enzyme which dissolves it. It is 
not improbable that this enzyme is pectinase, but this question is 
not yet answered. Should this really prove to be true, then the other 
question arises whether the so-called pectose of the central Jamellum 
of the tissues of the higher plants may not also be a cellulose 
modification, as it is also easily dissolved by pectinase. This view 
seems to be much more acceptable than the current hypothesis : 
the central lamellum should be the calcium salt of an acid, isomeric 
with arabin-acid. 

On the great similarity between pectinase and the seminase of 
the seeds of the Leguminosae, I already earlier directed the atten- 
tion. That the latter enzyme does not attack true cellulose is in 
accordance with the same property of pectinase. 


SUMMARY. 


With a not too limited species-conception Clostridium polymyxa, 
Granulobacter polymyxa, Bacillus macerans, and Bacillus asterosporus 
may be brought to one single species: Bacillus polymyxa. 

It is the only hitherto known aérobic spore-former, which, in 


287 


neutral sugar-containing media excites fermentation and thereby 
proves able to live as a temporary anaérobe. 

The chief products of the fermentation are carbonic acid and 
aleohol. At the aérobie life a little aceton results, evidently from 
oxidation of sugar. 

Anaérobie accumulation is possible in rye paste at 30° C. after 
short boiling. Aérobic accumulation takes place in dilute malt-wort 
or broth with 2°/, to 5°/, sugar, after heating at 85° to 90° C. 
or short boiling with much garden soil and cultivation at 15° C. 
by which B. mesentericus is excluded, whose growth minimum is 
at about 20° C. 

The general distribution of J. polymyxa in decayed plants and 
its occurrence in the bark of plant roots and of the nodules of the 
Leguminosae reposes on the production of pectinase, which dissolves 
the central lamellum of the cellular tissues. 

Bb. polymyxza forms much slime from sugar, which must be consi- 
dered as cell-wall substance. Without carbohydrates or polyalcohols 
its growth seems impossible, hence it develops but slightly on 
broth agar. 

The slime may serve as reserve food. 

Laboratory for Microbiology of the Technical 
High School at Delft. 


Mathematics. — “On the Light Path in the General Theory of 
Relativity.” By Prof. W. van pur Wovupe. (Communicated 
by Prof. H. A. Lorentz.) 


(Communicated at the meeting of September 30, 1922). 


In Ewstein’s theory the path of a ray of light is found by putting 
the condition that it is a geodesic null line in the four-dimensional 
time space'). If accordingly we represent the line element of this 
time space by 

ds*— 29, da, dx, . .. . . . . (i) 

; i,k 
the light path satisfies equally the equations of the geodesic as 
those of the null line 


ds 0 295 GOSS Rea eee (ces) 


As far as we know the remarkable relation existing between 
these differential equations, has not yet been pointed out. We shall 
prove that this may be expressed in the following way : 

a geodesic having one element, t.e. one point with the tangent at that 
point, im common with a null line, is itself a null line. 

In order to prove this we shall first give the equations of the 
geodesic a form different from the usual one (§1), as on account 
of (2) it is not desirable to take s for the independent variable. 
With a view to an «application which we shall give later on, we 
take one of the coordinates of the time space for the independent 
variable. 

We shall conclude by pointing out the (evident) physical meaning 
of the theorem. 


§ 1. If the line element is represented by 


ds* = Sg, dx, dx, , 
1,k 


the equations of the geodesic are 


— =) 27 


d?x, \ Aujda) da, 
|» \ds ds 


') From this there follows for the statical field (giz independent of the time- 
coordinate xo and go) =O for 1/0) the principle of FERMaAT for the minimum 
time of light in three dimensional space. 


De bdae’ fi 


289 


Curistorrer’s symbol !’ b 
vp 


has here the meaning : 


hu au 
teee['] 
b E T 


where g” is the algebraical minor of g,, in the g-determinant divided 
by this determinant, and 


Zl uu 1 0g» Odus Ogi. 
= = + = = 
Dot 2\0z. Ore Oz, 


As independent variable we chose one of the coordinates, e.g. «,. 
In this case 
dx, ; ds da, Grote edsiNe .axcy 33 d ity A 
ds “~ dx da Gerda dete ~~ (4) 


especially for a,= a 


x, ( ds sak dx, d*s 4! 
ds* \da,) ds dex, ee ae 2) 


lf therefore we multiply the former of the equations 


= 
12 ; 
ds dp. 


Y ds ds 


d?x, a 7 uu dx} Ag 


aa, = | Au) day da, 


ds? Me. ( 0 ds ds 


ds \? ls \? da, 
by iS). the latter by ) ie we find after subtraction by 
the aid of (4) and (4’) 


GG as Au Aw) dx, | day dx, 
— Jb = = S05 a oe ee O 
dhe v 0 \ da, \da, dx, 


0 py 
These are the equations of the geodesic which we had in 
view. Taken as the equations of the geodesic of a two-dimen- 
sional space (a surface in the usual meaning), they give 


d?v 22) (dv? 22 12 dv\? 

=e Head wae yy 
du iG) ah 1 | du 

3 al 11)\dv \11 

+( os aH Va Ws 


a well known form, which is often taken as the starting point for 
the discussion of the properties of this line. 


=——=\()), 


290 


la. 
§ 2. We multiply (5) by Gn and sum with respect to » and 9; 
Okie 
the equation thus found 


ax, Au 2 uj dx, | dx, dx,\ dx 
Eo (TS +, 2 || | — e | : *) 7=0 . (6) 
dg” Nae | » 0 \ da, |dx,dx,) dx, 
may be reduced to a different form. 
I.et us consider the first term: 


d*z, as 
Se ae dz,” 


AS 9.=9 we may att write ie 


1 Va, dx, dx, da, 1 d (dz, 
— 2 Qvo (: = se sli = = Qe Z a ; 
Zu. \da,*dz, dz, da: 2p | dx, \da, dz, 


In the second term 


’ | dx dx, dx, 
» \ dx, dz, dz, 


\Au 


we replace by its expression between the square brackets and 
Y 


apply a reduction 


> - Au |dx;, dx, da, eee 2p] dz) dity — dz, 
ea er ako Chante A, jasde, 2 Ogee 


= y [A] tendon 
A MyT T dx, dz, dz, ‘ 


7 1 (for, -e==) 
0 (for 9 Ar). 


According to the meaning of the symbols { |, we may replace 
the expression thus found by 


as 


= I Ie Ki 


1 s O9inda, dx, dx, 1 dx, dey dyn 
2 ur Ow, dx, dz,dz, 2 3, dx, da, da, 


The two former terms of (6) may therefore be combined to: 
lad dx) da, Wh GEY \ 
> in —— : 
2d@,i, de,dz, 2 dz,\dz, 
We write the third term 


Au 
= a | 


Ay /y)P » 


da, dx) diy dx, 
dx, dz, dz, dx, 


291 


Ss: diac, da, > " u dex) =) sa = ¥ : uw) da) bala 
yo da, dz, ru | 0 | dz, dx, dz] in 0 \ dz dx, 


so that (6) is transformed into 
2 pe 3 > ; 
uh (A a Baca " " 2 ees Ratan) 
2 dx, \dz, daryemaleO) \ dada, 


§ 3. Let us now define a line in time space by 
ai = Gi (ws 
where we require of the functions 7: 
1. that the line defined in this way satisfy the equations of the 
geodesic ; 
2. that in a definite point A 


ds \? de; di 
(=) = (see ae) 25 
dz, / A ik dz, dx, / 4 


Of course we also suppose that the coordinates w; are defined as 
uniform continuous functions of a2, and that also gik and its 
derivatives are uniform continuous functions of the coordinates, at 
least in the region in consideration. 

We have in this way taken care that the line defined by (8) is 
a geodesic and has a null element in A. As it is a geodesic 
each of its points satisfies (7); each w; being a function of a,, we 


may conclude that 
da (ads Ne ds \* Bey 0 
daa) = tas) Y=” 


where @ is a uniform continuous function of ap. 
Hence, along each geodesic 


ds \? ds \? ee ® (x9) dry 
—} =(—]e”® sw aie eens 18) 
dz, /P dz,) A 


by a, and p, we understand the values which «, assumes at the 
starting point A and an arbitrary point P of the line. 

However, we have also made the assumption that the geodesic 
in consideration has a null element in A. Accordingly here 


ds \? 
——= |) e=(. 
dx,)A 


On the other hand there follows from (8) that along this line always 


1. 3 
(=) = (i); 
dz, 


as 


292 


in other words that the line in consideration is a geodesic null 
line, which was to be proved. 


§ 4. Let «, be the time coordinate. In three-dimensional space 
in a point A an arbitrary direction is defined by giving definite 


day 


ratios to (d= 1, 2, 3). If inversely we assume these ratios as 


av, 


dar) .~ 
given, we can give such values to Te that the condition 
da 
0 


ds \? . da) dx, 
— | > 29,,— — =0 (Ayo 107 lero) 
du. “de, dz, 


dye 
is satisfied. 
The theorem which we have proved, has therefore the meaning: 
In three-dimensional space there passes a ray of light at any 
moment through any pot in any direction. 


Physics. — ‘Calculations of the effective permeability and dielectric 
constant of a powder.” By G. Breit, National Research 
Fellow U.S.A. (Supplement N°. 46 to the Communications 
from the Physical Laboratory at Leiden. (Communicated by 
Prof. H. KamEriLinGH Onnxs). 


(Communicated at the meeting of October 28, 1922). 


Introductory. 

The pure samples of some rare substances are available only in 
powdered form and show particularly interesting magnetic properties. 
For this reason it is desirable to know tbe relation between the 
measured and the true permeability of a powdered substance. 

If the susceptibility is small the effects of the demagnetizing field 
are negligible and the magnetization of any individual particle of 
the powder is the same as it would be if the particle were part of 
a solid block. Supposing that the particles are crystalline, the measured 
specific susceptibility is the mean specific susceptibility of a crystal 
provided in taking the mean equal weights are given to all orien- 
tations of the crystal. 

In the case of gadolinium sulphate at 2° K. the magnetization is 
considerable and the above approximation does not suffice. This fact 
has been realized by Prof. H. Kamertincn Onnes and a correction 
has been made by him’). Prof. Kamertincu Onnes expressed his desire 
to the author to see a more accurate correction. This forms the 
subject of the following pages. 


Approximations and statement of problem. 

In view of the random distribution of the principal directions of 
the individual crystalline particles the difference between suscepti- 
bilities in different directions will be neglected. This probably intro- 
duces an error in the calculations which however is likely to be 
small. 

It will be supposed that the applied field is so small that the 
magnetization is proportional to the field. Some of the results of 
the calculation are independent of this assumption as will be brought 
out later. 


1) Leiden Comm. Suppl. N°. 44a p. 10. 


Proceedings Royal Acad. Amsterdam. Vol. XXYV. 


294 


For convenience of notation the electrostatic problem of a powdered 
dielectric in an electric field will be treated. The results are trans- 
lated into the magnetic ease by substituting the permeability mw for 
the dielectric constant «. 

Our problem is to calculate the effective dielectric constant of a 
powder under the above assumptions as to the smallness of the field 
and the random distribution of the axes when the density of packing 
of the powder and the dielectric constant of the material of the 
powder are known. 


Definition of “effective dielectric constant’. 


Let us consider a portion of the powder which contains many 
particles and let us take the mean electric intensity and the mean 
electric displacement throughout this portion. (The mean being taken 
with respect to volume). We define: ‘effective dielectric constant” = 

mean electric displacement 


mean electric intensity 

We presuppose that this definition is unique which implies that 
the powder is sufficiently fine for otherwise it is not possible to 
include a sufficient number of particles without making the portion 
so large that the field would vary in it (from point to point) if the 
powder were replaced by a solid. 

Let us draw a spherical surface inside the powder. According to 
the well known treatment of polarized media the electric intensity 
inside the sphere is equal to the electric intensity due to charges 
inside the sphere plus the intensity due to charges of polarization 
on the surface of the sphere and plus the intensity due to charges 
of polarization on the outer surface of the powder as well as that 
due to charges outside and inside the powder. This means that the 
electric intensity 

Y ee dg E, AF E, 
where 

E; = effect of charges inside the sphere 

E, = effect of charges of polarization on the surface of the sphere 

E, = effect of charges of polarization on the outer surface of the 
powder + external field 

where ‘external field’ — field due to all real charges and the 
charges of polarization not belonging to the powder. 

Since each individual particle- is uncharged £; is obtained by 
summing the fields due to charges of polarization on the surfaces 
of the particles inside the sphere. 


295 


If EZ, should denote the average value of Z, throughout the sphere 
we have with a good approximation H,—= FE because the usual 


treatment of polarized media may be applied to # and the result 
is H, if the powder is fine. 

Let a certain volume be occupied by the powder and put in an 
external field ©. Then /, 47 € on account of the charges of polari- 
zation on the outer surface of the volume. It is for this fact that 
the correction has been made by Prof. H. Kameriincu Onnes. We 
shall suppose in what follows that this or an equivalent correction 
is made in the final interpretation of the experiment. In order to 
make such a correction however one must first obtain the effective 
dielectric constant and then operate with this constant just as one 
would in the case of a homogeneous medium. Thus e.g. it may be 
shown’) that the force on a sphere of radius a placed in a field 
of force given by H, + bz parallel to the OZ axis of a rectangular 
system of codrdinates having its origin at the centre of the sphere 


B : : 
and 2 along the radius @ perpendicular to the axis of z is 
i= =n) ! BE, where L,, & are constants and « is the dielectric 
é 


constant. Hence 
De ene et 
1 — Fas BE, 


Preliminary approximate solutions. 


(a) A space lattice of. spheres. 

Consider a space lattice of spheres the density of packing being 
not too great. We can get very easily an approximate solution for 
this case. Let us suppose that each sphere has its boundary removed 
so far from the surface of the adjacent spheres that the field acting 


1) Using equation (6) (to be derived presently) we find that the density of the 
fictitious distribution of charge is (using polar coérdinates with OZ as axis) 


act 1 [8 (e—1) 5 (e—1) 
(SE = (La in Ye EP 8 eS cos : 
GS Fig Bi, aay (or) 4 7 BaP, (6) | 
Hence the force 

ar 
EF = = [a + BoP, ow o|* BP, (os 8) + 
cos §—=—1 

d(e— 1) e—1 
ine ees P, (cos 8) | (es 6) ae 5 B. 


296 


on it may be considered as uniform. Then the sphere is uniformly 
3 «,—1 
dae, +2 
trie constant of the sphere and F' is the uniform field acting on 
the sphere. If g should denote the fraction of the volume of the 
lattice which is occupied by the spheres themselves, the average 
polarization is 


polarized, the polarization being F’, where «, is the dielec- 


Mie 3q &,—l 


= F. 
48,42 


Since now the effect of a uniformly polarized sphere at points 
outside the sphere is equivalent to the effect of a doublet at the 
centre of the sphere the contribution to / of the particles of powder 
situated inside the large spherical hole vanishes by a well known 
reasoning of Lormnrz') and his result for # applies here so that 


4a &,—1 
F=>E 4 go bot aoe 
1.8. 
ee E 
eeaae 1 
&,+2 
and 
__ 3q E Ol 
4x e, +2 4a 
aire 
where ¢ is the effective dielectric constant. 
Thus 
e—l & 1 : 
7s sn nk ish 
3 coe 
and letting 
ph q = 
a?) ee coe 8 ce (LA) 
we have 
e—l a 1 V 
ae ar . «a el 


Thus the effective susceptibility of a powder is not proportional 


1) H. A. Lorentz, Theory of Electrons, p. 308 


297 


to the density of packing but should be corrected by the factor 
1 


= 
It is worth noting that (1) may be written as 
e—l —é,—l + 
==) 2 (1") 
e+2 €,+2 


which means that if the powder is moulded in a sphere then the 
force on that sphere is a q'® part of the force which would be 
exerted on a solid sphere of the same radius. In other words each 
individual particle of the powder may be considered as acted on 
only by the external force. (I have seen a very direct and simple 
proof of this fact from Prof. Enrenrest). 

We see therefore that to within the approximations made so far 
the factor See used by Prof. H. Kameruincu Onnes should be 

rane 

used with the value of the density in the solid — not the powdered 
form. 


(6) A space lattice of spherical holes’). 


The case considered above may be expected to give a good ap- 
proximation if the powder is packed loosely. If it is packed closely 
a better approximation must be expected from a space lattice of holes. 

It is not necessary to treat this case independently because use 
can be made of formula (1) if it is remembered that in (1) & is the 
ratio of the effective dielectric constant to the dielectric constant of 
the space between the spheres of the lattice. Denoting by q as before 
the proportion of the volume occupied by the substance (i.e. the 
ratio to the total volume of total volume minus the volume of the 
holes) and leaving (14) unchanged we arrive at 


e— 1 1 

pbiaa dha (2) 

oa en il 

3 + 2d 

which may be also shown to be equivalent to 

e—l1 1 ' 
[= == “Si pn 

2 ie = sao 

1 + 2e, g 


1) The possibilities of this case have been pointed out to me by Prof. H. 
KameruincH Onnes and Dr. H. R. Wotrser. 


298 


From either of these formulas we find 
e—1 €é,—l 
Ane) ee Spd? 
ea 
3-20 
This formula is analogous to (1") in (a) and shows that to within 
the first power of Jd the force on a sphere having spherical holes in 
it is the same as if the sphere were moulded into a smaller sphere 
without holes. Thus the conclusions drawn in (qa) for the correction factor 
i 
— remain valid in this case. 
4x od 


cigeu 


(2") 


(c) Laminary structure of powder the directions of the laminae 
being distributed statistically. (See fig. 4). 


The electric intensity may be resolved into two components 
normal and parallel to the laminae respectively. 

(I) Normal component. 

Letting H#,, E,, h,, h,, &, €, be respectively the normal components 
of the field intensity, the thicknesses, and the dielectric constants 
of the interspaces between the laminae and the laminae themselves 
we have: 

FE, bt hb, Baa 


&—le enh hye) het 


Writing 
h, Ey + hy E,= (hy +h) B 
and letting 


= 


se 


E &£, 
&, 1 ta @,— 
we obtain 
es h, +h, a 1 
he het) p +g é, 
having let 


h, h, 
Te Lee 
This number ¢, is the effective dielectric constant for the component 
normal to the laminae. 
(Il) Parallel component. 
For this it is clear that the effective dielectric constant is 
hie, the, 
&> = ———_ 
h, +A, 
(II1) Both components present. 


eile 76 


Pp: 


=P + 9, 


The electric displacement is 7 (&, cos H, &, sind) where > is the 
ey 9 


angle made by the mean electric intensity with the normal to the 
laminae. Since the directions of the normals to the laminae are 
entirely arbitrary with respect to the direction of the mean electric 
intensity, the component of the electric displacement perpendicular 
to the mean electric intensity is distributed at random. The only 
component to be considered is then that parallel to the mean electric 


intensity which is re (En cos* J + & sin? J). The effective dielectric 
U3 


constant is 


ee — & 2€, 
& = &, cos* d+ &, sin 


Hence we get 


——t 1 + 2 pd 
q(,—l) 1+ pd | 
To within the first power of d this is the same as (2) or (1’) so 
that in this case the conclusions drawn as to a force on a sphere 


are still valid. Rewriting (3) in the form 


eee 1 (3' 
[= 0) renee 
3 + 2pd 
it becomes apparent that the value of « obtained from (3) lies between 
the values obtained from (1’) and (2). 


300 
Variable susceptibility. 


To within the approximations made so far the case of variable 
susceptibility offers no difficulty. Thus in the case (a) it was assumed 
that the field acting on each particle of the powder is uniform. 
Whether the susceptibility of this particle depends on the field or 
not its polarization is uniform and is such that the electric intensity 
I, inside the particle is 


where / is the intensity of the field acting on the particle and 
é,(/2) is the value of the dielectric constant of the material of the 


2 eee 
particle corresponding to /. If the mean field is #, #= H+ ae 


&,(2)—1 
4a 
simultaneous equations 


3 5 
(.+=-1) ey 
Pp P 


&, = &, (Z) 
The solution may be obtained graphically or otherwise. 
In the ecaleulations that follow the correction for variable suscep- 
tibility is more complex and will not be considered. 


and P= Hi. Hence EF and «, are the result of solving the 


The distribution of potential in a rectangular space lattice of 
dielectric spheres. 


In order to investigate the errors involved in the approximations 
we shall look for an exact solution in the case of a space lattice 
of dielectric spheres. The following notation will be employed: 

h = distance between centres of adjacent spheres. 

&, — dielectric constant of the material of the spheres. 

(7, 7, ~) = polar coérdinates of a point referred to centre of sphere 
placed at the origin. The polar axis is chosen along one of the 
rectangular axes of the lattice. 

(r,, 0,, ~,) = polar codrdinates of a point referred to centre of 
sphere whose Cartesian codrdinates are: 

(a, Y,;,2,) and whose polar codrdinates are: 

(R,, 9, ®,). 

The radius of each sphere is taken to be 1. The mean field is 
also supposed to be 1 and directed along the polar axis. 


301 
Polarization of single sphere in external field. 


Before proceeding with the solution of the problem it will be 
convenient to derive an expression for the state of polarization of 
a dielectric sphere placed in a known external field. Charges of 
polarization are induced. If the electric intensity due to these charges 
be #; and if the impressed electric intensity be /,, the total intensity 
is H—= #, + H;. Let us suppose that 4; may be derived from a 
. potential 


A}, PX (cos ‘) cos mp 
ia = ma (4) 
outside the sphere. Then it must be derivable from 
V= ZA r P (Cost cosm@tea ys 2s %- . ((d) 


nm 

inside the sphere since the potential is continuous at the surface. 
Denoting the components along the outward drawn normal by the 
suffix mn and referring to the state just inside the sphere by n, and 
to the state just outside by n, we have the boundary condition 

& (Een aa Ein) == Joe Ein, 
or 

(€,-—1) Ben = Ein, — & Ein, 

Using (4) and (5) 
(€,—1) Een = = (ne, +- 2 +1).An 


nym 


P (cos H) cosmp . . (6) 


Thus if E,, can be expanded in a series of surface harmonics 
the coefficients A” may be determined from (6) and hence the state 


of polarization of the sphere may be obtained. 
Derivation of expansion for En. 


In order to solve the problem it will be sufficient to express F,,, 
in terms of a and substitute the result in (6). 


0 


The average polarization of the medium being x we have 
p 
4nr A,° 0 mpm 
eet Icon SF — — > sv AP (cos 9,) aed mp, 
3h dr 1 nym n+l —T 


the first summation being extended over all the spheres inside a 
large sphere having its centre at the origin, the dielectric sphere 
situated at the origin being omitted from the summation as indicated 
by the accent. Using the notation: 


302 


m gn—n 
= gm 0 
mn om om 
ve = gm + Om 
E=a+iy, y= a—iy 
and letting 
= UB UG 5 5 5.6 3 th 


it may be shown that [see appendix formula (14)] 
cosm (p, P™ (cos D,) (—)" 2” by, 


aa a 
= Dio 2 Se id 
r+ (n—m) ! 5 : (= m) 


the differentiation being performed with respect to the end point of 
the vector 7, i.e. with respect to (7, /.¢). Thus 


_ 40 A,° 0 (2b ed 1 
1 1 + ——— }|cos } — -~ = Bee SE -—_—— 
3) 6h? Or \ nn=l,... (2— m) / A NCTA ELC iy a 


1 1 
where — has been subtracted from — so as to secure absolute 


Kk. ™, 
convergence of expansions that follow. Now 
1 1 er a(n) ae - 
zy a R, = ae Ri eCEESy) P" (cos 9) P™ (cos@,) cos m(p—®,). 
m=0,...n 


When this is summed with respect to R,, @,,@, terms in sin m ®, 
and all terms with an odd m drop out. Hence 


—)\n Qn § AS Die) in 

Abe AS 0 i ( ) m 44n . & 

Een =| 14+-— — ]cosd— pens, — 
. ( + 3 3) 0. alee ay, ets (cos Jeosung) 


where 
st ,@—e)! P* (cos @,) cos p®, 
(vty)! Rew 
Now it may be shown that {see Appendix formula (24)| 
Dr (7 PY cores ues (—)" ; (»+p)! pn PEAY" (cos?) cos(m+) —p 
n by, 2m (y+u—n-+m)/ Om+u 
which when substituted into the expression for E,, just found gives: 


4a A® 
En. =(1 Bi, a) (cos #) — 


(8) 


m 


bn (v+p)! (v—n) Ap SS pts (cos) cos(m+-m)p _ 


> n-+-m 2 
Bi Ong (n—m) (op—n $m) } be 
_s (ne, +n + 1) An P,," (cos ) cos mop 
tien - e,—l 


———<— es! a 


303 


in virtue of (6). Equating coéfficients of P, we have 


e,+2 4x 
(= SF) Bat + dat srt 648 4. Se) 


$ cos? O, — 4 
Ry 
order to obtain A® we are thus in need of Aj, A?, ete. For these 

it follows from (9) that 
[2s + e+ 242] dregs 5 (2s + 2p + 2)! Soctopte 
el! PON (28)/ (2p+-1)! 
(GSS seth ooo) 


where use is made of the fact that S$ =’ == O02 9In 


Api 


the upper subscript being dropped for the present. Writing 


e,—l Aosti : (2s + 2p + 2)! 
B= a = p= 
a s+ 2 Hale (2s + 1)/(2p + 1)! nm 
a 28+ 1 (11) 
Sopos¢2 = Op4s 
we have 
as = Bs = (8, p) G45 % (GSA ach ooo)e eta. (017) 
p=0 
or 
Be 8 5)(45,0). Osc} Bs.) (8y3P) Opts Bp, so) «7 --.(L2/) 


p=1 
Substituting for «, on the right hand side the expression which 
follows for it from (12') and proceeding in this manner indefinitely 
we obtain purely symbolically on changing suffixes: 


as = Bs (8,0) 6, + iS Bs Bs, (81 81) (811 9) Os+ts,,5, + 


s;=1 


ar BS Bs Bs, Bs, (8, $,) (8,5 8,) (s,, 0) Osts,, 5 +55, 59 + oe 


8], $g—=1 
+ © BBs, +Bs, (81) Girt): - Got Sn) Op.) Gray stent, ytty #3 
Situs P 
where 
Ox,y,2,. == Oz Oy Oz... Pe ae a) 
If the spacing of the lattice is large in comparison with the 
diameter of each sphere this expansion may be expected to converge 
rapidly. As a first approximation the first term will suffice giving 
Qn esrmeyeeOgeeos ss sw (LS) 
Using (10) and (11) we have for the average polarization P=A, h~$ 
and the effective dielectric constant ¢ 


304 


3 
e—1 = 4a P= a (14) 
fa Sg (Oa yee 
é,—1 1 


4a 
where ¢ = = h—> and denotes as before the proportion of the total 


space occupied by the material of dielectric constant &. 
So far we have considered the field only in the direction of one 
of the axes of the lattice. If the lattice is rectangular and not cubical 
the quantities 6, may be different for the three principal directions. 
In the case of a cubical lattice however they are the same. Since 
all the relations of the problem are linear the effective dielectric 
constant in a cubical lattice is independent of the direction of the 
field and may be thus justly compared with the effective dielectric 
constant of a powder. 
If the first approximation (13') is substituted for a, into (14) the 
approximate formula 
3q 


‘adits (14) 


&,—l 


—q— & (28+ 2)? 8B, 6. 
1 


is obtained. In the summation of this formula the density of packing 
enters through the quantities 6, and the intensity of polarization 
comes in through p,. The quantity ¢,—1 occurs in these to the 
first power. If the more accurate formula (13) were used higher 
powers of ¢,—1 would come in. Hence if the density of packing is 
kept constant and if deviations from the simple formula (1") just 
become apparent due to an increase in ¢, formula (14’) is the proper 
one to use. On using (11) it may be simplified to 


3q ‘i 
a = a (14") 
&,+2 anes 6q)\3 
ee (6 4 eS Fe 2)? og, 
pared (ce) Ae (2s + 2)? 6; (= 


=e . a . . . . 
where 6, is the value of os; for I= which is the maximum possi- 


ble q for the lattice. The quantities 6, are rapidly diminishing as s 
increases. Thus we find 
3 (46,)? = 0.0646, —_5, (60,)? = 0.00032. 
Writing 
4s 
—+42 

© 2s +1 6 
g= 274 4 2)'6 ton UWE AI 

1 a 


™ 


305 
we get on neglecting terms of higher order than the second in e¢,—1 
e—l &,—l (Ee, 1) ae 
Se Si pod | BN ork pig (GUA) 
Thus owing to the interaction among the particles of the powder 
the force on a ball made of the powder can no longer be considered 
as the sum of the forces on the individual particles independently. 
The increase of the force to within terms in (¢,—1)* is given by 
(e,—1)" 
3 
the model considered g' = 0.065 and the correction factor becomes 


the factor 1 + q. For the maximum possible value of q for 


eee tify OF Supp N'i44o is 0.09 f 
eata ihe quantity -~->, of Suppl. N°. 44a is 0. Ol 


gadolinium sulphate at 2° K. then since d was taken as 3 of the 
actual density the quantity ¢,—1 becomes 0.36 and the correction 
factor is 1.0028. Thus the effect discussed must be taken into account 
if the measurements of the force are made to within 0.3°/,. If such 
a correction is made it should be also borne in mind that even the 
simple formula (1") involves terms of the second order in the apparent 
\é—1) if it is solved for ¢, as may be seen in the following way. 

For small values of «,—1 we have q (e¢,—1)—=xF' where IF is 
the force and x is a constant of the apparatus. For larger values 
of «—1 this is not true but it is convenient to call the quantity 
&a_—1 defined by the above equation: “the apparent «—1”. If the 
sample is spherical and if the powder may be considered as the 
cubical lattice just discussed 


€,—l 1 at Eg—1 
q —— ory — — 
€,+2 (e,—1)? 3 3 
Lo eG 
3 
Hence 
l= eee ee ore emma? (a: 12 [Ce 1) (17 
a or a Ber oy =| 1+ 3 ct a (€a—1)? |(€a—1) (17) 
lauomesaco 


t 
1 
Thus ; occurs here together with the larger term —. 
q 


If the demagnetizing field is negligible as in the case of a thin 
long tube e—1—x/'=q (e,—1) where ¢ is the effective suscepti- 
bility. Hence by (14") 


&a — 1 
&,—_1= g aaa (Le) 


P q 
Ren (ely (ee— 1)? 
pe gee 


306 


If the sample has the form of a thin slab normal to the lines 
of force 
Gel > 
142 : 
pt i ees (eI) 


—1l= 


(17") 


Space lattice of spherical holes. 


From (14") we get for this case to within the second power 
of (¢, —1)’ 


e—1= - 


where p' is the same function of hasq'. The corresponding formula 
for the space lattice of spheres is 


q (e,—1) 


€ —— ; — 
142-1) — Fei) 


wp 

The term S thus tends to reconcile the two expressions. However 
for the case of touching spheres or touching holes the space lattice 
of holes has a higher ¢ than the space lattice of spheres even though 
q is made the same for both. This means that the continuous path 
of the flux between the holes contributes to a high value of the 
effective «. It thus becomes apparent that q and «, alone do not 
suffice to determine ¢ even if the structure is on the average isotropic. 
The correction in (¢,—1)? may therefore be never applied with 
certainty and an estimate of its amount is all that the present theory 
can offer. 


SUMMARY. 


1. The consideration of the effects of the demagnetizing field for 
‘various models of the powder shows that to within the first order 
terms the correction is the same for all models considered and may 
be expressed by the fact that the force on a sphere of the powder 
is equal to the force which would be exerted on the material if it 
were moulded into a solid sphere instead of. being powdered. 

2. Different models give results differing in the second order terms 
in the demagnetizing field. 


307 


APPENDIX. 
1. It is shown in Maxwet1’s Treatise that 
(m) —)r m 1 
Ve = Fo) gn-t-l_ Pci — , 
n ni n Le 
Now 
_m 2Qn i ( nm 5 
i — ent (n De . cos mP 
and 
meee an ! hem m 
; 2" (n—m)!n! ” 
Hence 


2 JEN (cos >) cos mB (—)r 2" =m 1 
= c 
gn (n—m)!o nr 


It is also well known that. 


1 

Or es 

‘Pp; 7 (—)" r 
pti ons ; en ‘ 


These two equations may be combined in: 


cosm® P,. (cos 9) (—)r 2” bd, po 1 ( 
pri ie (n—m) ! ae A) 
where 
Ue = IN set ==} 
2. To show that: 
pe Py (cos H) cosuP\  (—)™ (vt p)irr™ PET" (cos) cos (m+u)® (2 
F ( by Or (vt+u—n+m)! ae a 
We consider the following cases: 
(L). Lm = 0 


We must show that 
pl pn 
(v—n)! (oss (cos d). 


Proof. Using Lapnace’s integral 


oy (r’ P, (cos :7)) = 
02 


1c 
P, (cos 9) = — Jo J + isin J . cos PD) d® 
X 
0 


a ( ata 
we have r’ P,(cos 3) = — | (z +20 cos ©) ® where p=V 2? + 7’, 
ax a 


308 


whence the formula follows on differentiation. 
CEA)S i m0 
We must show that: 


DM (om P, (c08 9)) = —"" rm PM (c08 9). 2 co8 my 


‘ rit 
2m 


Proof. Since 9? = 4 we have 


aaa ee e = Sct 
p 2%? (pl)* (n—2p)! 
Operating on this with D? and observing that 
cos"—2m—2p oF sin®p 
* (2m zap)! 22” pl(m+-p)! 
the above written formula follows. An analogous formula holds of 


n! 
PP 5 (cos) = — sin & (—) 
P 


—m 9) 
“ 


course for the operator D*. 


(111). m0, bet 
Using (14) and (II), (24) is found. 
(IP). m= 0 


This is also verified without difficulty. 


Physics. — “On the Heat of Mixing of Normal and Associating 
Liquids.” By Dr. J. J. van Laar. (Communicated by Prof. 
H. A. Lorentz). 


(Communicated at the meeting of September 30, 1922). 


1. In connection with a study by J. R. Karz (published in ,,Ver- 
slag der Wis- en Natuurk. Afdeeling Kon. Akad. v. Wetensch.” 
Vol. XXXI, nos 5/6, p. 333—336) | wish to make a few remarks 
on the heat of mixing of liquids, also in reference to the quantity 
@/,2 (Or 2/5). 

Different authors, among others van per Waats and myself, made 
use of approximations some time ago, which seemed permissible ; 
but which gave no account, not even in approximation, of the heat- 
effect, which is sometimes very slight, especially for normal substances. 
For here the case presented itself that the neglected quantities 
((v—6)*? by the side of v*, p by that of 7/2) would give a term of 
higher order of magnitude in the results than that which results 
from the not neglected part. The latter term appears to be of the 
order of magnitude (b,/a,—6,Va,)’, whereas that of the neglected 
~ part — yielding a term with (p + 4/,2) Av — is of the order 
6,V.a,—b,V a, on aceount of Av; hence, when the difference of the 
critical pressures of the components is small, the neglected part 
will have a much greater value than the not neglected part. 

And besides: While the first part — referring to the change of 


the potential energy without reference to the contraction — will 
always be positive, the second (neglected) part — which is in con- 
nection with the volwme contraction Av — is nearly always negative. 


In ‘“quasi-ideal”” mixtures of two liquids (i.e. liquids the eritical 
pressures of which are about equal), the effect will nearly always 
be negate (ie. heat is berated), and not positive, as the earlier 
theoretical derivation indicated. In liquids the eritical pressures of 
which are not about equal, sometimes differ even considerably, it 
will entirely depend on circumstances (relation of the a’s and 6’s 
inter se, value of the mixing ratio x) whether the result will be 
positive or negative. 

In assuciated components, where Av can become much greater 
than in mixtures of normal components (generally the critical pres- 
sures also differ much more from each other), the above ratios will 


20 
Proceedings Royal Acad. Amsterdam. Vol. XXV. 


310 


be more greatly accentuated, and the negative term with (p + 4/,2)Av 
will predominate still more. 

Already Baknuis RoozeEBoom — now about twenty years ago — 
drew my attention to the insufficiency of the approximative expres- 
sion, but at the time we attributed this to other causes *), thinking 
that -— especially in quasi-ideal mixtures — the possible volume- 
contraction would probably be quite negligible. Not until 1912, when 
in a letter my friend Prof. Kremann at Graz put a question to me 
on this subject, was I led to carry out the perfectly accurate 
calculation of the quantity Av ’). 

In what follows I may be allowed to give the exact theory, first 
of all of mixtures of normal components. Here too the perfectly 
accurate derivation appears to be by no means more difficult or 
longer than the approximated derivation, and the result is almost 
equally simple. The same thing is found here as before with the 
exact derivation of the equations of the spinodal and the plaitpoint 
line*). There the perfectly accurate results are even simpler than 
the earlier approximated expressions. 


2. Heat of mixing of normal components. 
From the well-known expression for the total energy 


Pe lg ORL Ak oy. 
v 


in which the energy constant e' is = n,e', + n,e',, and the heat capacity 
at constant (infinitely great) volume k=n,k,-+-n,,, we find for the 
pure components: 


‘ 


a, 
ee =, ar ii armen te 


1 
° ' gs ° 
Cer 1 a oie 
2 


For the integral heat of mixing of n, gr. mol. of one component 
and n, gr. mol. of the other component the expression 


1) Inaccuracy of VAN DER WAaLs’ equation of state; non-validity of BERTHELOT’s 


assumption dj. = Vad, etc. But since then I have got more than ever convinced 
of the absolute validity (in liquids) of the said equation and B’s assumption. Of 
course a and } then have other values than in the gaseous slate, but this need, 
of course, not be considered here. " 

1) Later inserted summarized in his valuable — unfortunately too little known 
— book: “Die Eigenschafien der bindren Fliissigkeitsgemische etc.” (Sammlung 
(Herz) chemischer Vortrige Bd. 23, Stuttgart, Enke, 1916); see p. 170—171. 

3) These Proc. Vol. VIl, p. 646; Vol. VIII, p 33. 


311 


a a, a, x ; 
w= — Ley eae (O — TW ey wea) 
v v; v%, 
is at once found from 


w=e—(n, e,° + rn, e,°) 
Now 


a a a a a a 
— => — + | -—-— — SS SS AN 
v v, v Vo OF vv 


in which v, = n,v,° + n,v,°, and v—v, — A is written. 


Further 
a=(n,Va, +n,Va,)*, and from this follows: 
a a a a VAG oe VAS 
a(n, A+ 0,28) — mm! Las ; aD 
VU, v, Uv, On tne OF 
Hence: 
a. (7a, —v.*Va.-)* a 
ne We, F - T+ (p+ )av. a () 
Gn the BE: VV, 


Remarks. a. Formerly *) the following equation was written: 


— (S (ob) + p(v—b) — (x, +2) Rr), 
v v v 


on account of the equation of state. This gives: 


fe ok a) + p(v—b) — (n,+n,) re =< (1 = (=)) ar 
v v? : 
+ p(v—b) — (rn, + n,) RT, 


exe + (: + (nm, +7) r) T (1 = o") + pb, 


for which e=e’ + k’T—*/,5 was written — with an apparently 
perfectly justifiable neglect of some terms. Then we get: 


hence: 


(d, Va, i= b, Va,)° 
1s 
bb, b, 


- C a C ; 
It is seen that the very essential term — Av is omitted. 


v, 


b. We might also have written: 


fe 2 
z =" a +n oe n,n (vs cs Sea Zale, 
rel 2 1 73 ? 
v Vv, Vy, Vv, v, 
P : v dv ; : 
in which i, and v, = = For according to a property of the 
n n 
1 


1) Cf. among others Zeitschr. f. physik. Ch. 68, p. 219 (1908). 
20* 


312 


homogeneous functions of the first degree with regard tom, and n,, 
we have v= n,v, + n,v,. And further according to (a): 


oane Me ael f(s sn 


VU, v, 


Se fil Coy (CR ho) Sein (C=) ), 


w=n,n, (iM a Vege) ar (» a9 = .) n, Av, + (° i = 5 nal (1”) 


Vv, v, V, Vv, viv, 


which expression will at once appear to be useful. 
Here is v,—v,°= Av, and v,—v,°= Av, and evidently we have 
Av = v—», = (nv, + n,v,)—(n,v,° + n,v,°) = n, Av, + n,Azv,. 


dw dw 


For the diferential heats of mixing w, = and o,= > wenow 
‘ ny n, 


have from (1%)'): 


y a,.—v ; 3 0 
w, =n, Cs Y Sire Va) (=) sais (» is iH Van 
vv On, v v0," 


ae 0 /n, PP, Ya 
On, \v vy} oan 


“i, = Mes (v, (7a, ——or Va,) a (» Be a, :) Av, | 


vv, Pi 
Likewise ; teas ous (2) 
a es Ueioeeuls Ves) =F (» ae rf :, Av, | 
viv, Uv, 


1) In these differentiations many parts have not been taken into account. For 
in general v, and v are still functions of m, and ”;. But as the neglected parts 


in W, and wy can always be represented by 2; = and a ie , in which 2, 
On, On, 

just as w, will always be a homogeneous function of the first degree with respect 
to 2 and mo, necessarily 22, + 7,2 will have to be = 0, 7,20, + MgW, already 
being = w according to (2). Now also 7,2, + % 2% =2, hence 2 is identically =o, 
hence also z, and 2g. 

It would indeed not be difficult to show directly the disappearance of the parts 
z, and 2, which have been left out of account. As to 2, we get the result: 


1 a, 4 a, dv, dv, 
2 n, 5 n, = (» ae SP On, r 


dv, Ov : 
in which the last factor will disappear in consegence of ao — =s » asd ty) is: sa 
2 


1 
homogeneous function of the Oth degree with respect to the molecular numbers 


nm, and 9. 


313 


For liquids p may of course always be cancelled against the so 


much greater molecular pressure 4/,2. 
We will just mention that the earlier — inaccurate — expressions 
were: 
3 (6, Va,—), VYa,)’ aS 2 (Os Va,—d, Va,)° 
’ \ ae r| 7 . 
6°, b%, 


wn, 


3. Volume contraction with normal components. 

We must now try to find an expression for Av, and then also 
for Av, and Av,, in order to be able to substitute in (1) and (2), 
and to form an opinion of the order of magnitude of the different 
parts. As 

Av=v—v, =v — (n,v,° + n,v,°), 
we have also: 

Av = b —(n,b, + »,b,) + (v — 6) — n, (v,° — 6,) — 2, (v,° — 4,). 

Now 6=n,b,-+ n,6,, hence after application of the equation of 
state, there remains: 


(2, + n,) RT je dale n, RT 
Ny = 


P+ PE ape pp a)’ 
i.e. with neglect of p: 


: 3 
3 ) ° 
v v U 
, 1 3 
Av = RT | (n, + 2.) — — 2, —n, : 
a a, a, 
or 
, 
2 2 2 
— ) 0 Cape Z 
Av aa. a, | a n,) (2, v; ate Ny Vy ) 5 Oy LE Eh CEE rae N,V,” oa, | ai 


Ted 
+ —(n, + ny(2 Av (n, v,° + 2, v,°) + (a0), 
a 
as v= (n,v,° + n,v,") + Av. In consequence of this, with a— 
= (n, Va, fi nN, Va,)’ 3 


eo eS (2a (v—Av) + (A0}t) = 


T a 2 
== Ceo a,a,—(n,v,° a+ n30,° a,)(n,V a, +7,V «| 
aaa, 


which, worked out with neglect of Av by the side of 2v, and 
putting n, -+n,=1 at RT’, gives: 


ao(1 = a ~*) — 
a/,, 


314 


= ev 7 | ; 0” 9 yO oe 
= —nyn, ee + 2(n, + n,) v,° v,° + n,v,° } a, ay — 


. °° 2 9 0? oh VY a: 3 
N,v, a,° +2(n, v,° a, +n, v,° @,)V aa, + 1, v,° a, 
RT bas 3 
=— n,n,| 2, pens (v,°+20,")/a,—2v,°Va, }—v,° a,7} 4- 
’ 


+n frase core +21) Vay—2n' Va, )—0," 


2v,°o,Va,(v,°Va,—2,’Ya,) +4,(v,° “ata + 


| 


For the form between | | we may further write: 
na, (v,°Va, +0,°a,) —n,a,(v,°Va, + 0,°V a,) —2n,0,°a,//a, + 2n,v,°a, Ya, 
= — na, (v,° Ya, —v,° Va.) — nya, (v,° Va,—v,° Va,) + 
2a, Va, (n,v,° + n,v,°) — 2a, Ya, (n,v,° + nyv,°), 


so that we finally get: 


2RT RT 
ho(1 = =) —_ nn, (v,° Va, —2,° v)) | 
a/y aa,a, 
- (3) 


E v, (Va, — Va,) Va,a, — (na, + ,a,) 0,° Va, — 2,° va) | 


+n, pen (v,°Va,—2v,° Va,) + a, (v,°"a,—v," a,) 


RT 


nmlo'Va.—rVe) alos a,+v,’V/a,)a,—20,°a, a, 


= n,| —(v,° Va, + 0,” 4,) a, 4-20;° a Va, 


This almost quite exact result (only p has been neglected, and in 
the 1st member Av by the side of 2v) shows that Av will be of 
the order d= v,°Va,—v,’Va,, so that w consists of two parts, of 
which the first is of the order d* (ef. equation (1)), the second of 
the order d. When the critical pressures differ little, d is very small, 
and of the small heat of mixing w the second part (neglected before) 
will certainly predominate. 

In the case that the critical pressures differ little, expresion (3) 
can be considerably simplified. For then v,°Va,—v,°Va, = 0 can 
be put between [ ih and there remains: 


315 


aye 1" )= Boe eh (1 Hat a ee ee 
a/, a/y, v,° Va, Va, a, 


: ay? y v,°—v,"_, 
But because then Va, = — Va,, Va,—Va,= Vai 
Vr0 v, 


co GES GT 47S 
= = m,n, = =F v, —v, A a 
ence v ( aj, a), 1 Py ) ) 


vo 


As for ordinary substances in liquid state (below the boiling-point) 
a), TRT;,, and in the second member v, —v may be put, we find 
with r= m: 


Iie Pk 
N= =e n,n, (a- 2) = Oab creo) (G33) 


If eg. m='*/,, we have with n,=1—a, n,=z2x for Av the 
value */,7(1—wz)(1 —1) (v,°—v,°), so that the maximum contraction 
(at z='/,) becomes = */,,(1—1’)(v,°—v,°) — hence very small 
and of the order 1—\. 

With regard to the sign of Av it may be pointed out that 6, > 6,, 
e.g. 6,=6b, corresponds with v,° >v,°. Then a, is approximately 
= 6'a,, so that “/,, becomes = O%/,, or 7%, > Tz,. But from this 
it ensues that pz, is generally somewhat greater than pz,, in conse- 
quence of which 1—)” becomes negative. And the reverse when 
v,° should be <v,°. The quantity Sv will, therefore, nearly always 
be negative, in other words volume contraction will take place. 

With regard to the differential variations of volume Av, =v, —v,°= 
— a and Av,=v,—v,° = = from the approximated expression 

1 Yy 
(3a) follows, when ¢/, is considered constant in the correction term 
of the 18* member : 


3, 2RT 0. (n, vr, 
Ar,(1= =2RTn, (IV) (v,"—»,")—(*"*}. 
a}, On, 


In approximation v,° Ya,=v,°Va, was taken, so that a, is = 


0 0 
v, v v 
= — ve / Un ; 1 rs o 
=,Va,and Va =n, Va, +n, Va, =) a(n, +m, =e ay 
2 


3 2 


: i) 0 n,v° v, 
In consequence of this becomes = — = 
0 a on Gti 


e 


v, 0 (n 1,0," N,v, 
ee | in which — ee ea =. Hence we have 
a, On, \v, = OF 


316 


0 (rv Ta iy Fi vie 
2 2 2 . . 
—{ — | =n, — == ih ; therefore with the same approxi- 


mation as (3a): 


2RT 2RT 
h»,(1 — = )=: — n,* (1—V) (v,°—2,°) 


*/» @/v49 
and ORT’ ORT = S.sraeea) 
dn,(1 — —_\= ays n, 7(1 —V) (u,°—v,°) | 
We now duly get again n,Av, + n,Av, = Av,, because 
v, ae v 
n,n,” — + n,n,?7 —=n, n, — 
a a a 


4. Substitution of (3%) in (1). 
We get for w, after substitution of (3¢) in (1), with omission of 
the external pressure p: 


@fVarntVay «thm | oven 


Wi Ne — 7 v8 v,° ba 123 p NN, 0 Va 1 fv,° v,°); 

or 

w= nn, E Viel Vie as */,m  (%_'V.a,—0,"V4,) (v,°—,*) |, 
Teas 1—?/, m Vitae 


when ”/,, Va is substituted for Va,. With m='/, andv=v,, this 
passes into 


Vor, 


SSS al" °Va,—, ‘Va °Ya,—v,’Ya,) — aC ove} 


The factor */, is, of course, somewhat different, when m= Be 
is not —'/,. When the critical pressures are equal, the foregoing 
factor is =O, hence also the total heat of mixing. But when these 
pressures do not differ too much, the first term between [{ | will 
all the same be small with regard to the second, and in approxi- 
mation 

a art (v,° Va,—,° Va,) (v,°—2,°) Ya . . (59) 


Grohe? ws 


may be written. 
But however this be, we shall always be allowed to write: 


w= nr,'n, ——_.— 3 Ww 


or, a5 vv, = 1,0," ate 15,” = (lL—a) 0," at xD, = v," i av y— v,") = 


ANS erat) HO 
= v,°(1+ rz), when ss ane =—— Ny (ence zs =1+ r) is put, and 
Vv, v, 
with B (78 
(v,°)’ 
a va (1—z)*\ a 
ets (1—2) Se OL Se a en en) (6) 
(l+r2) (1+ 7) (l+,r2x) (14+ ra)? (1+7) 


the old expressions, but in which @ has now a somewhat different 
value than before, and will also be dependent on the temperature 
(through m). 

When in approximation 


a 
o— 


Av=—Av 
v 


vv, 
is written for (1) with omission of the first part, which is generally 
much smaller, we get approximately : 

w a 
eae (7) 

If the critical pressures of different substances do not diverge too 
much, also the values of %/,s do not lie far apart in mixtures of 
different pairs of substances, and we shall find values of at least 
the same order of magnitude for the quotient aa a result to which 
also Mr. Katz came experimentally in his latest paper (loc.cit.) ') — 
at least as far as volume-contraction and heat of imbibition of 
amorphous and crystalline swelling substances is concerned. That 
the ratios there are quite analogous to those of liquid mixtures is 
owing to this, that when one of the components is sold, it must 
first be reduced to the liquid state, whence the pure heat of melting 
of this components is simply added to w. But if Av predominates, 
also this heat might be omitted with respect to the second part. 

At any rate we shall never find exactly “/,. for ~/s,, because the 
omitted part can never be entirely disregarded. For this reason also 
the values of ~“/,, will differ somewhat, even with almost equal 
values of @/,2, which was also found by Karz. 


1) The curves of Fig. ! and 2 are no hyperbolae, but oblique parabolae, 
a(l—z) a 

ltre 14r 
the integral heat of mixing (i.e. 1—a gr. mol. of J + 2 gr. mol. of JJ) would 
be a pure parabola. If, however, 2° is not =v ,°, the top of the parabola will 
have been displaced somewhat to the side of the component with the smallest 


as according to (6) wis = . If r were = 0 (%° = v,°), the curve of 


molecular volume, as is easy to verify. From %/ax = we find v=1:(1+V 1 +7), 
which gives x=1/, for r=0, but x <1/ for 7 >0. (vQ° > v"). 


318 


The values of ¢/,2 in our above formulae always refer exclusively 
to the liquid mixture, even for solid components, for as we already 
remarked above: this solid component must first be thought liquid, 
so that after all we have always to do with quid mixtures. 

Now that through the formulae derived by us above, the absolute 
values of w and Av are known, which Mr. Katz so eagerly desired, 
the problem has become clearer. Also when the components should 
be associated, everything remains essentially the same, as I will 
shortly show in a concluding paper. But then the preponderating 
influence of Av will still be more pronounced, in consequence of 
the great variation of volume on dissociation of the double molecules. 

And finally as regards the “important as yet undiscovered prin- 
ciples of the laws that govern molecular attraction” — I believe 
that this principle too was solved long ago'). This subject will also 
be discussed more fully in our concluding paper. 


Tavel sur Clarens (Suisse), September 1922. 


1) Compare my papers in These Proc. Vol. XVIII N°. 8, p. 1220—1235, and 
following numbers; in the Journ. de Ch. physique 14, p. 1 et seq. (1916); in the 
Z. f. anorg. und allg. Chemie 104, p. 57—156 (1918); in the Ch, Weekbl. of 
1918 (p. 1124); in These Proc. Vol. XXI N°. 5, p. 644—655, and the J. de Ch. 
ph. 16, 411 (1919), which possibly have escaped Mr. Karz’s notice. 


Histology. — “On the Regeneration of Sensitive End-corpuscles 
after section of the nerve’. By Prof. J. Boeke. 


(Communicated at the meeting of September 30, 1922). 


During the process of regeneration of the motor endplates of 
striated muscles we are in a position to observe not only that the 
nerve-fibers put forth new shoots again and unite with the muscle- 
fibers to form new end-plates, but also that all the surrounding 
tissue elements: the connective tissue as well as the muscle-fibers, 
the nerve-sheaths and the axis-cylinders of the nerves themselves, 
play a part in the regeneration process and are instrumental in 
ensuring its success. 

In the case of sensitive nerve-endings it is more difficult to observe 
this procedure: 1° because there is a greater variety in the shape 
of these endings than in that of the motor end-plates, 2° because 
many more varieties occur side by side in the same environment, 
and 3° because sensory endings generally offer greater difficulty in 
establishing the relation between the nerve-fibers and the surrounding 
cells than motor end-plates do. 

Now in the cere of the duck’s bill there are two sorts of 
sensory end-bodies, viz.. those of Granpry and Hersst, which are 
very well adapted to such an investigation by their simple, well- 
defined structure. 

We examined the regeneration after cutting the nerve. The ope- 
ration was well sustained by the animals and in a short time the 
wound was healed in primam (among 24 cases one inconsiderable 
suppuration) without any injury to the animals. 

After 4—5 days the severed nerves were completely degenerated ; 
nothing was left of the axis-cylinder except a few granules staining 
brownish black by Birrscnowxy’s method. After some days these 
also disappeared. 

An alteration of Granpry’s tactile cells or of Herpst’s core-cells, 
described by Gastorowski years ago after cutting the nerve, consisting 
in shrivelling of the cells and bulging and wrinkling of the nuclei, 
I have not been able to detect. In agreement with the aspect of 
the soles of the motor endings the protoplasm became more coarse- 
grained, swollen, while the impression was given that in the core 


320 


of Herpst’s corpuscles there were more nuclei than the normal 
corpuscle presents. There also seemed to exist a slight increase in 
the number of the capsule-cells of Granpry’s corpuscles. 

While regenerating the nerve-fibers follow the old nerve-courses 
(which have changed into strands of Bincner), and pass again into 
the primary corpuscles. It seems, however, that all along also new 
corpuscles, especially Granpry’s corpuscles, are formed, in which 
process sheath-cells (lemnoblasts) grow larger and become tactile 
cells, as Hertnga has established as to embryological development. As 
soon as the nerve-fibers have reached the tactile cells of GRANDRY, 
they branch out, grow sinuously round them, always embedded in 
the protoplasm of the capsule-cells and at length force their way 
between the tactile cells. Directly after this the neurofibrils begin to 
branch, broadening reticulations appear, which gradually spread 
between the tactile cells, first as a delicate retiform structure, after- 
wards as a close-mesh network. In this way the whole interspace 
between the two tactile cells is occupied again by a net-shaped 
neurofibrillar nerve-plate. 

Two things strike us here as being remarkable: 

First of all that in the beginning of the process of regeneration 
the nerve-fibers bend round the tactile cells in various convolutions 
and ramifications, but that in the following stages (after 2 or 3 
months) this process is less pronounced, so that gradually the normal 
condition asserts itself in the same way as with the motor end- 
plates; secondly that neither the nerve-fibers themselves nor their 
terminal branches and terminal broadening ever run freely, but 
always remain enclosed in the protoplasm of the conducting cells 
and the capsule-cells, and that directly when they are within reach 
of the tactile cells, a peculiar network is formed around them, 
inside the protoplasm of the tactile cells, which could also be demon- 
strated, in complete distribution, in the normal corpuscles of GRANDRY ; 
lastly that here the process of regeneration of the intraprotoplasmic 
network shows itself first round the end-branches (end-reticulations 
and end-knots) of the nerve-fibers and then appears to extend gra- 
dually over the whole extent of the flat tactile -cells. The whole 
regeneration-process takes two or three months. 

In the case of Hersst’s corpuscles the in-growing nerve-fibers also 
follow the old nerve-tracks. At their point of entrance into the core 
of the corpuscle we see also here that the nerve-fiber not only 
proceeds linearly into the protoplasm of the syncytially connected 
celss of the core, but also that it throws out its branches and passes 
with many convolutions through the protoplasm, so that the aspect 


win 


321 


Fig. 1. GrRANDRY’s corpuscle. 36 days Fig. 2. GRANDRY’s corpuscle, 46 days 
after cutting the nerve. Initial stage of after cutting the nerve. Complete 
the surface-enlargement in the neu- regeneration, double growth round 
rofibrillar apparatus of the nerve- the tactile cells. Longitudinal 
threads that grow round the tactile section. 


cells. Transverse section. 


Fig. 3. Fig. 4, 

GRANDRY’s corpuscle. 42 days after the cutting of the nerve. Transverse 
section of the same end-body at different planes. Splitting of the in-growing 
nerve-thread. Intrusion between the tactile cells, formation of a protoplasmic 
network (receptive substance, periterminal network) round the end-buds of 
the neurofibrillar nerye-apparatus. 


322 


of the whole structure becomes much more complicated than that 
of the primary nerve-fiber of the normal Hurpst-corpuscles. However, 
here also the normal relations gradually assert themselves. I have 
not been able to ascertain whether new Hersst-corpuscles are forming 
in the course of the regeneration process. 

Round the inner core in Herpst’s corpuscles are disposed a large 
number of connective-tissue lamellae, separated by lymphspaces. 


Fig. 5. 


Transverse section of a Herpst-corpuscle, with a nerve-thread that not 
only branches out in the protoplasm of the cells of the core, but proceeds 
from there into the connective-tissue lamellae round the inner core, where 
it continues its growth. 42 days after the cutting of the nerve. 


These lamellae are connected by means of cellular processes, thus 
forming a whole. 

Now in watching the regeneration it may be repeatedly observed 
that the nerve-thread, which has passed into the inner core of a 
Herest-corpuscle and ramifies in the protoplasm of the core, does 
not remain enclosed here in its entirety, but that some of the end- 
branches leave the core and intrude into the tissue of the connective- 
tissue lamellae. This then is the very place to see quite clearly, 


323 


that these nerve-fibers do not force their way into the lacunae 
between the connective-tissue lamellae, but that they lie in the 
lamellae, enveloped by protoplasm, and remain there. This envelop 
must decidedly partake of the nature of connective ussue. This 
observation, therefore, is in perfect harmony with what could pre- 
viously be established for the neuromuscular spindle of striated 
muscles. In them also the in-growing regenerating nerve-threads 
could be seen moving through the protoplasm of the connective- 
tissue cells of the capsular space, which cells have developed into 
a conductive-tissue. 


Utrecht, August 1922. 


Chemistry. — “Heterogeneous catalysis and the orientation of adsorbed 
molecules”. By Prof. H. R. Kruyr and C. F. van Duin. 


(Communicated at the meeting of September 30, 1922). 


In a previous communication’) we published investigations on the 
relation between the adsorbtion of reacting substances an the velocity 
of the reaction, with the object of coming to a better understanding 
of heterogeneous catalysis. In these investigations we found, that by 
giving coal to the reacting system a decrease of the velocity sets 
in, even in cases, where undoubtedly an increase of the reacting 
components in the surface layer takes place. 

In accordance with the theory of 1. Lanemuir*) and W. D. Harkins’) 
concerning the special condition of molecules, which are situated in 
surface layers, we tried to explain our results by the assumption 
1. that adsorbed molecules bave partly lost their mobility and con- 
sequently a great deal of the possibility of meeting and reacting 
with other molecules, and. 2. that. adsorbtion can cause positive 
catalysis only in the case, when the molecules are adsorbed in such 
a way that the number of effective collissions increases. 

That adsorbtion in itself can have a decreasing effect was found 
when studying a monomolecular reaction, viz. the transformation of 
racemic dibromo-succinnie acid into bromo fumarie acid and HBr‘). 
The results are given in the tables I and II. 

Evidently a marked decrease in the velocity occurs. 

We discussed in the paper cited above, that a positive contact 
catalysis can be expected only in the case, when the reacting group 
is turned away from the adsorbent and towards the surrounding 
liquid. With charcoal as an adsorbent, and water as milieu, all 
electrically polar groups will be turned towards the water; we 
therefore had chosen the reaction of @ dibromo-propionic acid and 
KJ (formation of acrylic acid, KBr and J,). As might have been 


1) Rec. trav. chim. Pays Bas 40, 249 (1921). 

8) Journ. amer. chem Soc. 39, 354 en 541 (1917). 

8) Journ. amer. chem. Soc. 38, 2221 (1916) and 39, 1848 (1917). 

4) Cf. Hotmpere, Journ. f. prakt. Chem. 84, 145 (1911) and Zeitschr. f. physik. 
Chem. 79, 147 (1912). 


325 


TABLE I. Without coal. TABLE Il. With coal. 
Time |c.c. NaOH) conc. k Time |S mee er pas conc. k 
in oot? |. m_ | mono- in ' 10 a 10 cc! in 72. | Mono- 
min. |p. 10 cc.|'" 499 | mol. min. ox coer: Cees ‘| 1 400 “mol. 
0| 20.22; 19.98 — 0 18.91 20.22 | 19.98 — 
1371 21.53 17.36 |0.000103 1372 19.89 | 21.20 18.02 |0.000075 
2991 22.70 15.02 095 2992 | 20.87 | 22.18 | 16.06 73 
4288 | 23.57 13.28 095) 4311 21.29 | 22.60 15.22 63 
6771 24.88 10.66 093 6788 | 22.12] 23.43 | 13.56 57 


expected, we then have found and accelleration of the reaction. We 
repeated these experiments in a 'CO,-atmosphere and in the dark 
room to avoid complications. The result was almost the same: 
without coal we found k — 0.000123 and when coal was added 
k = 0.000149. 

The place of the polar groups in dibromo-propionic acid is however 
not symmetric; the possibility remains that the COOH-group exerts 
a more vigorous orientating influence than the Br groups and con- 
sequently the latter will not be in a most favourable condition. A 
better result could be expectod therefore in the case of the reaction 
of dibromo-succinie acid and KJ. A comparison between the 
formulae 

HC—CH—COH en HOC—CH—CH—COH 

Br Br O O Br Br O 
will elucidate this immediately. Moreover, the stereochemical confi- 
guration suggests a still better arrangement in the case of the 
mesoform than in that of the racemic. In the tables II] and 1V we 
give the results obtained with the racemic, in the tables V and VI 


TABLE III. TABLE IV. 
Racemic-acid without coal. Racemic-acid with coal. 
Time |c.c. thio! conc. k | | Time | c.c. ge. ecu] ia cone. k 
in or “ mono- in 40 4 “i mono- 
min. 40 /300 | mol. min. |not corr.| corr. /800 | mol. 
0 0.08 19.92 — 0 Na[527/ 20.12 19.92 a 
790 1.82 18.18 |0.000116 7716 11.72 14.57 14.37 |0.000421 
1392 2.99 17.01 113 1380 8.90 15 11.55 395 
& mean 0.000115 k mean 0.000408 
21 


Proceedings Royal Acad. Amsterdam. Vol. XXY. 


TABLE V. TABLE VI. 
Meso-acid without coal. Meso-acid with coal. 
Time |c.c. thio | cone. | k Time | c.c. 15 c.c. J“) cone, k 
in | wee mono- in 40 4 mono- 
min, | 40 | /800 mol, min. |notcorr.| corr. /800 mol. 
0} 0.06 19.94 —~ 0} 18.21} 20.14) 19.94 _ 
289) Wil 18.89 |0.000187 292 | 14.45 | 16.38} 16.18 |0.000716 
516 |) 2.12 17.88 189 582 | 11.20] 13.13 | 12.93 744 
| 806 | 2.83 17.17 186 809 9.47 | 11.40 |) 11.20 713 
| i i 
k mean 0.000187 k mean 0.000724 


hose with the meso-acid. The initial concentration of the acid was 
/,o u., that of KJ 2n.; work is done at 25° centigrade, in CO,- 
atmosphere, in the dark room; 1 gramm of coal was added per 
100 cem.; in the experiments with ‘coal 10 cem. of the reacting 
mixture were poured into 20 cem. of thio-solution of 0.02525 n.; 
be titration was done with a J-solution of */,, n. 

These results, shewing a. great accelleration of the reactions, 
fully support our theory. 

We have still other expirience, which is in, accordance with this 
theory. Dr. C. F. van Duin wil give presently a detailed paper in 
Recueil des Travaux chimiques des Pays Bas. 


Utrecht, van “t Horr-laboratory, 


St. Andrews, United College of St. Leonards 
and St. Salvador 1922. 


Geology. — “Fractures and Faults near the Surface of Moving 
Geanticlines. IL. Abnormal Strikes near the Bending-points of 
the horizontal projection of the Geanticlinal avis.” By Prof. 
H. A. Brouwer. 


(Communicated at the meeting of September 30, 1922). 


In a previous paper') we have pointed to the occurrence of 
considerable transverse fractures near the bending points of the hori- 
zontal projection of the geanticlinal axis, which phenomenon has been 
explained by velocity differences on either side of these bending 
points. 

Another phenomenon that may be observed near the bending 
points is the occurrence of older strikes, inclined or normal to the 
horizontal projection of the axis’). This may be seen in rows of 
islands if the strikes in some islands do not coincide with the main 
trend of the islands. It is of great ‘interest for determining the 
precise movements of the rows of islands, as will be shown in the 
following discussion. 


The row of Islands Sermata-Islands, Babber, Tenimber-/slands. 

In the islands Letti, Moa, Luang and Sermata the principal strikes 
are sometimes more or less parallel to the direction of the row, 
e.g. in Letti. 


Fig. 1. 
1+:+s+ Horizontal projection of the geanticlinal axis (schematic representation). 
—— Older strikes and coastlines. 


In Moa some strikes are N.N.E. to N.E., so these are different 
from the direction of the row; in Luang the permian strata are 


1) These Proceedings XXIII, p. 570, 
*) H. A. Brouwer, The horizontal movement of geanticlines and the fractures 
near their surface. Journ. of Geology. XXIX, 1921, p. 560—577. 


21* 


328 


intensely folded, with strong differences in strike and dip. If we 
construct the geanticlinal axis, as is generally done, with right 
angled bends, near Babber and near the southmost island Selaru of 
the Tenimber-Islands, so that the geanticlinal axis between these two 
islands is below the surface of the sea, the Tertiary strike in Babber 
(N.N.E.) is about normal to the direction of the row. 


The connection of Halmahetra with the Pelew Islands. 

The soundings between these islands do not go against the 
assumption that the prolongation of the Northern Peninsula ‘of 
Halmaheira via Morotai towards the Helena-reef has a more or less 
east-western direction and bends in a more or less north-eastern 
direction towards the Pelew Islands. Even if considerable depths 


A. 


HALMAHE:R 


Fig. 2. 
.+.+. Horizontal projection of the geanticlinal axis (partly hypothetic). 
— Older strikes and coast-lines. 


should exist where the E-W. prolongation of Halmaheira’s northern 
peninsula is supposed to be, these depths may be the result of gaping 
fractures, that may exist near the bending-point. The known strikes 
on Morotai are in the direction of the longer axis of the island and 
are oblique to the supposed direction of the geanticlinal axis. This 
conception renders the resemblance between the outlines of Celebes 


329 


-and Halmaheira more complete. The difference between them consists 
chiefly in the eastern part of the northern peninsula of Halmalheira 
being covered by the sea. 


The row Formosa— Riukiu- Islands. 

The prolongation of the Sakishima-group is generally considered 
to be linked to North-Formosa’'), also by authors whose interpretation 
of the known facts differs from the one that will be put forward 


Fig. 3. 
Explanation of Fig. 2. 


lower down. The older strikes in the major part of Formosa are 
N.N.E. approximately parallel to the longer axis of the island. In 
North Formosa, however, their trend is about E—W, and tbey are 
cut off by the eastern coastline. In the Sakishima-group of the Riukiu- 
islands the strikes are irregular and are oblique or normal to the 
trend of the row of islands, while in the major part of the Riukiu 


1) S$. YosHiwara, Geologic structure of the Riukiu Curve ete. Journ. Coll. of 
Science, Tokyo. XVI. Part I, 1901. 


330 


Islands as far as Kiusjiu the strikes are again about parallel to the 
direction of the row. This example seems to be similar to the two 
preceding ones, but the areas near Babber, as well as those near 
Morotai, from which this analogy might appear, are covered by 
the sea. In Formosa the bending of the older strikes is visible 
and moreover it can be seen that locally near the bending point of 
the horizontal projection of the geanticlinal avis the older strikes are 
normal, or approrimately so, to this projection, while on either side 
they are parallel to it. 


The movement at the surface of horizontally moving geanticlines. 

In another publication we have already pointed to the difference 
in speed and direction of the movements at different depths’). The 
points, which were originally on the same vertical line, will in a 
later stage form an irregular curve in space. If the rate of movement 
has a vertical component, the vertical movement near the surface 
will be influenced by the vertical movement at greater depth. 

The complicated horizontal and vertical movements, which differ 
already at a comparatively short distance, will cause new portions 
of the surface to form the crests of the moving geanticline. The 
direction of the older strikes with regard to the new geanticlinal 
axis in a subsequent phase of the movement, will depend upon the 
rate of movement at greater depth and that near the surface and 
upon the rate of erosion. 

If the forees, which cause the movement of a geanticline, of 
which the highest parts rise above the sea-level as rows of islands, 
are deep-seated, the vertical movements will cause the uplift or 
subsidence of the islands, while the rate of horizontal movement 
at greater depth may differ considerably from the rate near the 
surface. We distinguish two extreme types of movement: 1° The 
horizontal movement near the surface is equal to zero. 2° The horizontal 


movement near the surface is similar to the movement at greater . 


depth. In general neither of the extreme types will occur. In the 
first case no horizontal fracture-movements will take place at the 
surface, and straits generally correspond with a depression, islands 
with a culmination of the geanticlinal axis in a given stage of the 
movement. 

In the second case the islands as such move ina horizontal direc- 


1) H. A. Brouwer, The horizontal movement etc. loc. cit. 
Id. The major tectonic features of the Dutch East Indies. Journ. Wash. Acad. 
of Sciences, 1922, p. 172—185. 


—— 


331 


tion, and straits may originate near the fractures without a subsidence 
of the geanticline along the axis. The movements near the surface 
are not equal to those at greater depth. But we suppose an extreme 
case, in which, considering broadly, the portions near the surface 
move at the same rate as those at greater depth. 


The vertical movement and the effect of erosion. 


Considering that during the movement erosion will continuously be 
at work in the portions above the sealevel, it will generally be possible 
to compare in the terminal phase the direction of the geanticlinal 
axis with the direction of the exposed older strikes. In case of a 
brief and not very intensive erosion, the tectonic details of a more 
plastic deformation at greater depths, are still invisible. The intensity 
of erosion decreases if, as in many rows of islands, the deform- 
ation of the geanticline takes place near the surface of the sea, 
and it is especially, when the vertical! component of the rate of 
movement is great, that the tectonic details, which have been formed 
by a more plastic deformation at greater depth will soon be visible. 


Rectilinear old strikes and curved geanticlinal axis with a bending- 
point in the last phase of movement under consideration. 
The two extreme cases, mentioned above are: 


1. No horizontal movement at the surface. 

In the case represented by fig. 4 the old strikes cut the geanti- 
clinal axes of the terminal phase on either side of the bending-point 
of A’B’ at an angle of about 45°, while nearer to A’ and Bb’ the 
older strike will gradually coincide with the new geanticlinal axis. 
If we assume that in the portions AC and DB, the movement has 


soreee- Older strike. 

AC B=horizontal projection of the geanticlinal axis inthe initial 
stage of the movement under consideration. 

A‘ 0! PD! B'= Ibid. in the last phase of the movement under 
consideration. 


332 


taken place without velocity-differences and normal to the geanticlinal 
axis, gaping fractures will nevertheless be lacking in the portion C’)’, 
and in the case of a row of islands a strait will correspond witha 
minimum of the vertical projection of the geanticlinal axis. 

2. Horizontal movement at the surface, corresponding with the 
movement at greater depth. In the portion C’D’ gaping fractures 
will be formed which — in so far as they occur near the surface 
of the sea — may be visible as straits between the islands. 

In the positions A’O” and B’D’ the old strikes will not differ 
from the direction of the new geanticlinal axis; to what extent they 
will do so in the portion C’D’, will depend on the movements near 
the surface. If these movements are non-rotational, differences up 
to 45° will oceur; with rotation of the portions of the fractured 
surface the differences may be approximately zero. 


Curving older strikes with a bending-point, and curving geantichnal 
axis with displaced bending-point in the final stage. 

One of the numerous variations of this more general case is 
represented in Fig. 5. 


wereeee = Older strike. 

ACDB and A’C’ D’ B’ = horizontal projection of the 
geanticlinal axis, resp. in the initial-, and the terminal stage 
of the period under consideration. 


1. No horizontal movement at the surface. In the final stage the 
old strikes are nearly all oblique to the geanticlinal axis, near the 
bending-point even approximately normal to it. Straits will correspond 
with depressions of the geanticlinal axis. If the geological structure 
changes chiefly in the direction vertical to the old strike, islands of 
highly different structure will in some places be located side by side. 

2. Horizontal movement at the surface corresponding with that at 
greater depth. When, in the terminal stage of the considered period 
of movement, the points A, B, C and D have reached respectively 


ee se eee 


333 


A’, B’, C’ and D’, gaping fractures will appear all along the line 
A’ C’ D’ B’, which may have helped to form straits. If during their 
displacement the parts near the surface had at the same time 
rotating movements, the angles between the old strikes and the 
geanticlinal axis may approach zero in the final stage. 

Explanation of the abnormal strikes near the bending-points. 

The abnormal strike of the island of Babber (fig. 1) may be 
accounted for by assuming that the deformation of the geanticline 
at greater depth has been attended with similar horizontal movements 
near the surface, so that e.g. the geanticlinal portion near the surface 
of the Tenimber Islands may originally have been situated N.N.E. 
of Babber, while these parts have since been displaced considerably 
relative to each other in a horizontal direction. 

When assuming that no horizontal movement has taken place 
near the surface, the abnormal strike in Babber may also have 
originated from the great velocity-differences in a horizontal direction 
at greater depth, with this difference that the submarine geanticlinal 
part between Babber and the Tenimber-Islands is not disrupted 
near the surface. If the bending-point is the horizontal projection of 
a point that gives a minimum in the vertical projection, it may be 
that near it a large part of the geanticlinal axis is below the sea. 
In that case data will be lacking for a comparison of the present 
morphology with the older tectonic structure of the parts on either 
side of the bending-point. 

Likewise the connection of Halmaheira with the Pelew-Islands is 
covered by the sea in a considerably area on either side of the 
bending-point, but in Morotai, where the older strike is oblique to 
the geanticlinal axis, the geanticline still emerges from the sea, 
while here the resemblance of the coastline to that of the neigh- 
bouring part of Halmaheira points to horizontal movements of the 
islands as such. In the row Formosa-Riukiu Islands (Fig. 3), unlike 
in the preceding instances, the bend of the older strikes is not 
covered by the sea, which facilitates a more correct explanation of 
the phenomenon. The dips in the older formations of the Taiwan- 
mountains in Formosa point to WNW. movements, those in North- 
Formosa to southward movements, those in the major part of the 
Riukiu-Islands to S—E movements. It is evident therefore, that 
already during the older phases of the orogenetic process, there was 
a tendency to form a bending-point between Formosa and the Riukiu- 
Islands. Similar movements during the youngest phase of the mountain- 
building process gave origin to numerous fractures, e.g. those which 


334 


eut off the E- W_ strikes of North-Formosa at a right angle and 


separate the Sakishima Islands from each other and from Formosae 

According to our conception of the differences in character and 
vate of movement at different depths, the absence of islands between 
Formosa and the Sakishima Islands may be looked upon as resulting 
from the formation of gaping fractures, in connection with the 
velocity-differences in a horizontal direction at the surface near the 
bending-point, and from a minimum elevation of the geanticline near 
the bending-point of the horizontal projection of the axis. The ab- 
normal strikes of the Sakishima-Islands find an explanation in the 
assumption of movements, such as have been referred to above in 
the discussion of a geanticlanal movement with curving older strikes 
and with a displaced bending-point in the final stage (Fig. 5). The 
movement can be described only in broad outlines, the details can- 
not be derived from the visible facts. Thus the strikes on the Saki- 
shima-Islands have no constant direction, and differences occur between 
the strikes of the older and those of the more recent deposits. Near 
the bending-point, however, irregular movements can be expected, 
while at the same time the rate of vertical movement, and econse- 
quently the rate of erosion must in a high degree have influenced 
the present-day. tectonic structure. 

The abnormal strikes of the Sakishima-Islands have been explained 
differently by von RicutHoren '), who speaks of transverse subsidence 
causing an abnormal dip of the strata in connection with his ex- 
planation of the origin of the mountain ares of Eastern Asia by 
tensional and not by compressional stress. In contradistinetion to 
this interpretation by vertical movements, we have compared the 
features with those of other belts of islands and find an explanation 
of the abnormal strikes near the bending-points of the geanticlinal 
axis in considerable horizontal movements, which have already been 
discussed by us for various geanticlines in connection with other 
features. 


1) F. von Ricuraorgn, Geomorphologische Studien aus~ Ost-Asien, Ill. Sitz. 
Ber. Akad. d. Wiss. Berlin. Phys.-math. klasse. 1902, p. 944 et sec. 


Chemistry. — “Cycle Derwatives of Mannitol’. By Prof. P. van 
Rompureu and J. H. N. van DER Bure. 


(Communicated at the meeting of October 28, 1922). 


Many years ago the researches on the decomposition of the for- 
mates of polyhydric alcohols, and also those on the 1.3.5. hexa- 
triene, induced one of us (v. R.) in collaboration with Mr. Van Maangn, 
to study the action of formic acid on mannitol.') 

After they had succeeded in preparing the hexaformate of mannitol 
it appeared against expectation that on being heated this substance 
yielded no hexatriene or only traces of it; on the other hand it 
yielded a product of the formula C,H,O, though in small quantities. 
This product, which boiled at 107 —109°, had already been obtained 
by Favconnier’), together with isomannide, on heating mannitol with 
formic acid. 

Also the tetraformate of mannitane and the diformate of iso- 
mannide were obtained by heating mannitol and formic acid, both 
in pure state. Fauconnier") found already, that by heating the 
diformate of isomannide only carbon oxide was evolved, with 
formation of isomannide; when on the other hand the former was 
heated, carbonic acid gas was formed, and again the oxide C,H,O 
was obtained. 

The following constants were found for this latter product, which 
is very strongly levo-rotatory. Bp. 107°, dif =0,9226, np, = 1,3567. 
With bromine it gives a liquid dibromide, C,H,Br,O, di2?— 0,8622, 
Bp. 15 mm. 118°.5. A tetrabromide could not be obtained. 

Reduction with hydrogen, according to SaBatinr and SENDERENS, 
gave with C,H,O, both at 110° and at 180° a product of the 
formula C,H,,0, which did not boil constantly under ordinary pressure 
but at 16° at 23 mm. Hence only 1 mol. of hydrogen had been absorbed. 

In virtue of the decomposition of the di-formate of isomannide, in 
which only carbon oxide is formed, (so that it may be assumed not to 


1) Van Maanen, Diss. Utrecht, 1909. 
4) C. r, 100, 914 (1885). 
8) Bull. Soc. Chim. N.S. 41, 125 (1884). 


336 


contain two vicinal OH-groups) van RomBurcn and van MAANEN 


OH 
is 2a) aaa 
proposed among others the formula CH,.CH.CH.CH.CH. CH, for 
-__9——_!_ | 
OH 


OH 
] Oz 
isomannide, and CH,.CH.CH.CH.CH .CH,OH 


be be 
for mannitane, the formate of which gave only carbon dioxide. 
The compound C,H,O might therefore be represented by the formula 
CH,.CH: CH.CH. CH: CH,, hence it would be a-vinyldihydrofurane. 
| O I 
In 1917 Wuypaus and Tomic') too studied the compound C,H,0O, 
and could obtain by its reduction with hydrogen under the influence 
of palladium, an addition of two mol. of hydrogen, so that C,H,,O 
was formed, which substance according to them should be identical 
with a d-hexylene oxide described by Lipp’), in which not a 5-ring, 
but a 6-ring occurs: CH,.CH,.CH,.CH,.CH—CH,, so that the 
| 0 | 
original oxide would have the formula CH : CH . CH: CH. CH. CH,. 
| 
They concluded to the identity of the two saturated oxides by 
the equality of the boiling-point, both of the oxides and of the di- 
bromides derived from them. Winpaus rejects the possibility of the 
oxide being a furane-derivative, because then no asymmetric formula 
would be possible. This argument is, however, not valid with regard 


to the formula drawn up above. 

It has appeared from investigations on the action of ozone on 
the oxide C,H,O, undertaken by Mr. Bruins in the Utrecht Labor- 
atory after the publishing of Winpaus and Tomicu’s paper, that 
in this reaction only carbonic acid, formaldehyde, and formic acid 
could be found, but no products in which a CH,-group occurs, 
which pleads against Wunpavs’s formula. This, however, did not 
give. a rigorous proof for the  a-vinyldihydrofurane-formula. To 
obtain perfect certainty, we have followed another course. 

First of all by reduction of C,H,O0 with bydrogen of a pressure 
of two atmospheres in the presence of palladiumsol the saturated 
1) Géttinger Nachrichte Math. Phys. Kl. 1917, S. 462. 

4) B. 18, 3275 (1885). 


337 


oxide C,H,,O was prepared. We used for this purpose an apparatus 
as indicated by Skita’), in which the process of the reaction can 
be easily followed. During the fractionation the substance poly merizes 
partially, so that a perfectly pure product only can be obtained 
at the expense of considerable loss. 

In spite of careful purification the possibility exists therefore that 
a small quantity of unsaturated product is left behind. 

The substance was optically inactive, and showed the following 
constants : 


bp. 103°—106° dij 0.8693 n, 1.42797 
(analysis: found C 71.8 H12,3; cale. C 72,0 H 12,0). 


In the way indicated by Lippe loc. cit. we have further prepared 
the d-hexylene oxide, with the following constants: 


bP 106°—106°.2, d'° 0.8617, n, 1.41887. 


Since on reduction a-vinyldihydrofurane must yield y-hexylene oxide, 
we have also prepared this oxide according to WouLGrmutH’), who 
however, only gives its boiling-point, viz. 106°—108° at 770 mm. 

The following constants were found: Bp,,, 106°.5—107°, di? 0.8609, 
Dp 1.41685. 

The corresponding bromides were obtained by treatment of these 
oxides with the 8-10-fold volume of hydrobromic acid (48 °/,) in a 
sealed tube for 1 to 2 hours at 100°. The 1-5-dibromo hexane boiled 
at 15mm. at 105°—108° (analysis found Br. 65.3°/, calc. 65.5), the 
1-4-dibromo hexane at 106°—108° at 15 mm. (Br. found 65.4). The 
boiling-point of the di-bromide obtained from the reduced oxide C,H,,O 
was 106°—110° at 14 mm. (Br. found 65.6). It is evident that from 
the equation of the physical constants, both of the oxides and of 
their di-bromides, no conclusion can be drawn about the structure 
of the reduced oxide C,H,,O, unless there are large quantities of 
the substances at our disposal. It was, therefore, necessary to try 
to obtain crystallized compounds. An attempt to prepare crystallized 
benzoates of the glycols corresponding with the dibromides did not 
meet with success. The action of piperidine on the di-bromides, on 
the other hand, in which quaternary ammonium bromides were formed, 
had a favourable result. 

In analogy with von Braun*), who made act 1-5-dibromo pentane 


\) B. 45, 3595 (1912). 
2) C.r. 159, 80 (1914). 
3) B. 89, 4347 (1906). 


338 


on piperidine in excess, we prepared, from the 1-5-dibromide, the 
a-methylpentamethylene piperidinium bromide: 


CH,—CH, CH,—CH, 
ou,” iit Nou, (l) 
"\cH, on 1 Non, =H“ 
| Br 
OH, 


By recrystallisation from alcohol-ether it is obtained as a white 
crystalline substance, melting above 290° (Br found 32.63, cale. 32.5). 

In an analogous way the 1-4-dibromide yielded the a-aethyltetra- 
methylene piperidinium bromide: 


CH, —CH, CH,—CH, 
Ny qq cual eae 
—cH” | \CH on, 
Br 
C,H, 


This substance melted at 270° corr. (Br 32.58 found, 32.5 calec.). 

The dibromide obtained from the reduced oxide, C,H,,O, treated 
in the same way, yielded a substance melting at 269° (corr.). (III). 
A mixture of this substance and the preceding one melted sharply 
at 269° corr. 

Hence the 1-4-hexane dibromide and the dibromo derivative of 
the reduced oxide are identical. 

_Moreover we prepared double salts with platini chloride which 
likewise present the same analogy in their melting-points and in 
those of their mixtures. 


From (I) (C€,,H,,NBr), PtCl, Pt. found 23.4 
M.P. 247° corr. 

From, [I 9M P2607 ay A 3. 42be0 

From) Ti iePa 2592 aie i O23 


eale. 23.5 


Mixed melting-point I and II 246° corr. 
ns > Il and III 260° 


Here again appears the analogy between the compound obtained 
from the 1-4-oxide and that which was prepared from the reduced 
oxide, C,H,,O. Consequently this reduced oxide may reully be 
regarded as a-ethyltetrahydrofurane and the unsaturated oxide C,H,O 
of Fauconnier as a-vinyldihydrofurane: 


339 
Cre CH 


| | 
CH, CH—CH = CH 


NioZ 


The place of the double bonds in this compound is now exactly 


known. The substance being optically active, an asymmetric carbon 
atom must be present in it; a formula, e.g. as the following: 


O 
CH,—CH,—C CH 
Oa 
would not satisfy, as has also been remarked by Wiunpavs. 

As a-vinyldibydrofurane is formed from mannitane tetra for- 
mate, it is now possible to draw up a structure formula for the 
anhydrides of mannitol, viz. mannitane and isomannide. 

We then arrive at the following scheme for mannitane: 


OH 
ee a i ae 
CH,—CH— CH —CH—CH—CH,OH. 
keen 
OH OH 
In connection with the spatial formula of mannitol: 


OH OH 
are Pee 
in bn 
We see that as soon as the oxide-ring is formed between the C- 
atoms 1 and 4, the OH-groups at 2 and 3 will be at the same 
side. Besides the molecule contains two OH-groups situated beside 
each other at 5 and 6 (in perfect accordance with the pyrogenic 
decomposition of the tetra-formate, in which formic acid and carbon 
dioxide are split off from OH-groups placed beside each other), so 
that here a possibility must be for the formation of a di-acetone com- 
pound. In fact this compound was obtained as a colourless substance 
crystallizing in glossy leaflets, melting-point 155° (analysis C 58.83, 
H 8.38; calculated C 59.0 H 8.2). 
The conductivity of boric acid will also be increased greatly by 
mannitane. *) 


1) Béesexen, Rec. 40, 553 (1921). 


340 


Through the formation of a second oxide ring, we then arrive at 
the following formula for the second anhydride 


OH 
: 0 No 
CH,— CH —CH—CH—CH—CH, . 
| | O | 
OH 


The places of the OH-groups here are at 2.5; hence no acetone 
derivative can be. formed, nor will the conductivity of borie acid 
be raised. On treatment with acetone and 1 °/, hydrochloric acid 
the isomannide was actually recovered. The results of the measure- 
ments of the conductivity are recorded in the following table: 


Capacity of the vessel 0.4106. 
Conductivity of the boric acid 0.5 mol. Litre 30> 10-6 = K3. 


In water In boric acid sol. 
—| Ki—(K,-+Ks3). 
A. | W. |Ko><10-®| A. | W. Kx 


Mannitol 500 | 5660 72.5 | 500] 1037) 396 | 294 
Mannitane 500 | 3240 126.8 | 500} 440) 933 176 
Isomannide 480 |11000 34.4 4.4 


The concentrations were 0,2 mol./Litre. 

After deduction of the conductivity for water 3 >< 10-°, we 
find therefore that iso-mannide in a very small, quite negligible 
degree increases the conductivity, whereas this increase for man- 
nitane exceeds that of mannitol more than 2'/, times. 

Of the forgoing we may conclude that the structure of the un- 
saturated oxide C,H,O is proved, likewise that of mannitane. The 
given formula for isomannide seems to be exceedingly probable. 


Utrecht, Org. Chem. Labor. of the University. 


Chemistry. — “J/n-, mono- and divariant equilibria’, XXII. By 
Prof. F. A. H. ScHREINEMAKERS. 


(Communicated at the meeting of October 28, 1922). 


Equilibria of n components in n-+1 phases, when the quantity of 
one of the components approaches to zero. The influence 
of a new substance on an invariant equilibrium. 


For the equilibrium : 
E=fF,+ F,+...4 Frys eibacs bs 1151), carbs tat l) 


of x components in »-+ 1 phases, as we have seen furtherly, are 
valid the equations: 


Z. (04; OL; = 5 


wherein 


and further: 


OZ, OZ, OZ p44 r 
= waters —_ = K, 
dz, * da. Oan44 | 
(3) 
0Z, 02, OZ 44 P | 
—_— = Sn ere a SI 
dy, OY, Ont ati 
to which still must be added the corresponding equations for the 
variables z,z,...u,u,... etc. As it is apparent from the number 


of equations (viz. n*-++ ») and the number of variables (viz. n? + n+ 1), 
this equilibrium is monovariant, consequently, in the P, 7-diagram 
we represent it by a curve, which we call /. 

When in this equilibrium / all phases with constant composition 
contain together only n—1 of the m components, so that in these 
phases one of the components f.i. X is missing, then, in the phases 
with variable composition the quantity of this component \ may 
approach to Zero. 

Then the equilibrium / passes into an equilibrium, that we call 
E\(x=0) which consists of n—1 components in »-+ 1 phases and 
that, consequently is invariant; in the P,7-diagram it is represented 
therefore, by a point which we shall eall 7(2— 0). This point is 
the invariant terminating — or beginning — point of curve £. 

22 

Proceedings Royal Acad. Amsterdam. Vol XXV. 


342 


As we do approach the quantity of the component X to zero, 
we put again: 


Z,=2', + RTz, log x, Z4,=2',+ RT, log x, . (4) 
etc. In similar way as we have done formerly, now we find: 
0Z' 
H; dT — V;dP + RT x; + yid ee at eee) 
ey a 
ti Al heryte eter ei(f0 t=) 
%,— Uy, %, Uy Uy ©, + - + - Mnf = Mnfi%, + 9. (6) 
0Z' 0Z' 0Z', 
da eg? Sg eK, ee) 
dy, dy 2 Yn+1 : 


To these equations (7) must be added the corresponding equations 
for the variables z,z,... u,u,. The sign d indicates that there 
must be differentiated with respect to all variables. 

Now we add to one another the +1 equations (5) after having 
multiplied the first with A,, the second with A,, ete. Then we obtain: 

= (QH). dT — 3 (av). dP RT Bias) ayaa , 
L Sz) (ak ys 2 ee ital 
Now we put: 


> (2) = 0) of AHA, +... + Angi = 0 
= (av) ==0 of Ayz, + aye, +... An Xp = 0 | 
= (Ay) =0 of Avy, +4,y, +... + Anti Ynt1 = 0 
ete. but not > (AH) and S (AV). 
Then we have n equations, so that that the m ratio’s between 
a,4,..- dn41 are defined. The reaction: 


AF aF, aaa a Oe nL) 


which may occur in the monovariant equilibrium /, when the 
quantity of the component X is infinetely small, is, therefore, also 
defined. We shall call this equilibrium, which differs extremely 


(9) 


little from H(¢= 0) the equilibrium /# (Lim «= 0) or shortly the 
equilibrium # (av). With the aid of (9) now (8) passes into: 


dP\ (aH) ‘4 
(2) ee 


wherein 4, 4, are defined by (9). 

Consequently the direction of the tangent to curve # in its 
invariant point of beginning or terminating 7(«—o0) is defined by 
(11). The relation (7) (XIX) is, therefore, true also when the quan- 
tity of one of the components approaches to zero. 


343 


Now we put: 


= (4) = 0 conseq. 4, + 4, +.---+ ani = 0 

Sa(ayyi— 0 4, Aye, ayy eH ns Yt — 9 

Gea UN tears es joe de. ot eek tn to Ants Zn —— ON (EZ) 

= (AV) — 0 pra ld 8 ASV, +--+ Ant Vapi——0 
but not S (4x) and = (aH). The n relations between A, A,... angi 
are then defined again. Those relations now define the isovolumetrical 
reaction in the invariant equilibrium («= 0). 

Now it follows from (8) 

RT > (iz) 
S(H)y- 
wherein the index V indicates that 4, 4,... 2,41 must be calculated 

from (12) consequently from the isovolumetrical reaction. 
Also we may put: 
= (2)= 0 conseq. 4, + 4, 4+ --..+ Angi = 0 
Say 0; 5, Ay + Ay, eS. + np Yn = 0 | 
poe (He P08 Aye 2, es yan Anti n44 = 0 }..(14) 


(a7), =— (13) 


ey ——O 9,5 AH, 4- AHS... FE Any Bata = 0 
but not D(ax) and S(2V). The relations between 4, a, ... Anti 
are, therefore, defined and by this also the isentropical reaction, 
which may occur in the invariant equilibrium L(«@—0). Now it 
follows from (8) : 

__ RTS (az)y 


GS osSanyae (15) 


wherein the index H indicates that 2, 2,.... 4,41 must be calculated 
from the isentropical reaction, therefore from (14). 

From (11), (13) and (15) follows the relation 

DAV). S(AA)y. (ele + [(AH). SAV). S(Ax)y =O (16) 

While the direction of the tangent to curve Hin the point 7 (« = 0) 
follows from (11), formula (13) is determining whether this curve is 
going from this point towards heigher or towards lower temperatures 
and (15) is determining whether it is going from this point to higher 
or lower pressures. 

We may express all this also in the following way. When we 
add a new substance to an invariant equilibrium, then it becomes 


monovariant, the partition of this substance between the different 
22* 


344 


phases is defined by (6). By (13) is defined whether the temperature 
is rising or falling; by (15) is defined whether the pressure is in- 
creasing or decreasing. 

We write the isovolumetrical reaction: 

A, PF, ay, ee eA Ky + dea Fon 
wherein all reaction-coefficients have been taken positive. Now we 
have: 

= (47)7 = 4H, + dots Fg +....—4,H,—41,H,—.... 
D5 (i! \p= Ag €q + Agta Loti + ..-- —'d, Wa == A, RS Abe 

Now we assume that we have written reaction (17) in such a 
way that it proceeds on addition of heat from the left to the right; 
consequently (A/7/)) is positive. In order to determine the sign of 
= (Av) we have to dissolve 4, 4,... from (12) and we must know 
the partition of the new substance between the different phases ; 
this may be found from (6). 

In some cases the sign of & (Ax)y is known, however, at once 
without this ealculation. When f.i. the new substance occurs only 
in one or more of the phases, which arise in (17) on addition of 
heat, consequently, in #, Fj41..., then ie 7, = 07/07 — 0 
and, therefore = (Ax)y is positive. It follows then from (13) that 
(dT), is negative. 

When, however, the new substance occurs only in one or more 
of the phases, which arise in (17) on withdrawing heat, then 
XqgXg4i-.. are zero, so that (4x)y is negative. Then it follows 
from (13) that (d7’)r is positive. 

When, however, the new substance occurs in both groups of 
phases, then only a calculation more in detail may decide on the 
sign of 2(Ax)y and consequently also on the sign of (d7’),. 

Now we represent the isentropical reaction also by 

A, Fy da Ry tee ne gh e:-h Aa 

However we have to take ‘in mind, that A, 4,... in this case, 
must not be dissolved from (12) but from (14). Consequently in (18) 
2,4,... shall have not only other values than in (17), but one or 
more of them may have also other signs, so that they must be 
transferred from the one part to the other. Now we have: 

2 (AV) = Ag Vg + Agi Vegi +.... —4,V, —4,V,—.. 
= (A «)H=dg Wy ae Cee Cel a 6 oa Ly Hy A, uv, — 

Now we assume that reaction (18) is written in such a way that 
it is proceeding from left to right with increase of volume. Conse- 
quently (4V)z is positive: When the new substance occurs only 


345 


in one or more of the phases which arise at increase of volume, then 
(ax) is positive and, in accordance with (15) therefore also (dP);. 

When, however, the new substance occurs only in one or more 
of the phases which arise on decrease of volume, then 2(Ax)); is nega- 
tive and therefore, also (dP), is negative. 

Hence we may deduce the following rules: 

When we add a new substance to an invariant equilibrium 
EA\(x=0) then a monovariant equilibrium / occurs, which we 
represent in a P,7-diagram by a curve 4; when the new substance 
occurs only in one or more of the phases, which arise at the iso- 
volumetrical reaction on addition (withdrawal) of heat, then the 
temperature is lowered (raised); consequently curve £ proceeds 
starting from its invariant beginning-point towards higher (lower) 
pressures. 


In some cases we may also deduce something on the direction of 
curve # in its invariant beginning-point in the following way. We 
assume that the new substance which is added to the invariant 
equilibrium : 

Pi Ot Fy oe oe ig te Fight + ---- + Fifi 
occurs only in the phases /,4;,.../,41 and, therefore, not in 
F,, F,...F,. This is surely the case when F,...F, are phases of 
constant composition. When we take away from the equilibrium 2 
the phases 41... /,41, than we keep an plurivariant equilibrium 
F,...F; this is represented in the P,7-diagram by a plurivariant 
region. As curve / must be situated in this region, hence follows 
the said-above. In the special case that the new substance occurs 
in one of the phases only, curve / coincides, therefore, with one 
of the monovariant equilibria of the equilibrium («= 0). 


Before applying those considerations to some cases, firstly I will 
draw the attention to some points, which have been already discussed 
before. When we know of the isovolumetrical and isentropical 
reaction the ratio of the coéfficients 4,4,.... and also in which 
direction those reactions proceed on addition of heat or on increase 
of volume, then we shall say that those reactions are known quan- 
titatively. When we know, however, only the signs of 4,4,.... 
and also in which direction the reactions are proceeding on addition 
of heat or on increase of volume, then we shall say that the 
reactions are known qualitatively. Then we only know which phases 
are at the one side and which at the other side of the reaction-sign. 


346 


When we know of each phase of the invariant equilibrium #(«=0) 
the entropy, the volume and the composition, then with the aid 
of (12) and (14) we may define the isovolumetrical and isentropical 
reaction quantitatively. Consequently we are able to draw exactly 
the direction of the different monovariant curves in the ?, 7-diagram, 
we call it a quantitative P,7-diagram. 

When we only now both reactions qualitatively, then we can 
define only whether the monovariant curves proceed, starting from 
the invariant point towards higher or, lower temperatures and towards 


higher or lower pressures; but then their situation with respect to 


one another is still undefined; this we call a qualitative P, 7-diagram. 
We take for example the reactions: 
| EOE ie 3) ASD gees AH>0 AV=0 
j Ae TEN 0) Voy a Db AH=0 AV>0 
of a ternary invariant equilibrium. The first is, according to the 
supposition AV —0, the isovolumetrical reaction and it takes place, 
according to the supposition 4 H > O from left to right on addition 
of heat. It appears from A H—O and AV > 0 that the second 
one is the isentropical reaction and that the volume increases from 
lef to right. 
In accordance to our former considerations, now we have: 
FL+ FPF, 2F,+Ff,4+ F, AH>0 A Viz=0 
PIPE) | (4) (F 3) 


: (19) 
towards lower 7’| towards higher 7’ 
Further we have: 
Fa ele ee AH=0 AV>0 
EE) a Nahe) (F,) (FY) 
(20) 


towards higher P| towards lower P 

In accordance to our previous notation, herein is: 

(FJ=F,4+F,+F7F,4+ 7% . #)=f,4+ 7,+ *,4+f,, ete. 

Now we know qualitatively the P,7-diagram; we know viz. that 
from the invariant point curve (/’,) is going towards higher 7 and 
lower P; curve (/,) goes towards higher 7’ and: at the same time 
towards higher P, ete. 

Inversely we can also find from a qualitative P,7-diagram the 
qualitative isovolumetrical and isentropical reaction. When weknow 
fi. that the curves (/) and (#,) go towards higher temperatures 
and (F,) (Ff) and (f,) towards lower temperatures, then we have 
to construe (19) in the inverse direction viz. from the bottom to the 
top, in order to find the isovolumetrical reaction. 


——_— 


347 


When we know that (/,) and (F,) go towards higher tempera- 
tures, and (F,) (/,) and (F,) towards lower pressures, then we find 
at once, by construing (20) in the inverse direction the isentropical 
reaction. 

Firstly we shall apply those considerations to a simple case viz. 
to the addition of a new substance to the invariant unary equili- 
brium H(w«=—0)=F4 L+ GCG. The P,7-diagram may belong to 
two types, viz. when the volume decreases, on melting of the solid 
substance, then fig 1 is true; when the volume increases, then fig 2 
is valid. The regions in which occur the phases Ff, L and G are 
indicated by the same letters, but in a circle; the curves are repre- 
sented by (F), (LZ) and (G); in accordance with our notation is 
(P)= L + G, ete. 

When we add to H(7=0) a new substance, which occurs only 
in the liquid, then the monovariant equilibrium H— + L4G 
arises; when we take away from it ZL, then we keep the equilibrium 

Curve E coincides therefore in figs 1 and 2 with curve (ZL) of 
the invariant unary equilibrium (2 — 0). 


Fig. 1. Fig. 2. 


When we add a volatile substance, then we must take away 
from the monovariant equilibrium the phases 1 and G, so that we 
keep F only. Therefore, curve / must be situated in the region F’, 
as f.i. 2a, 7b and tc in the figs 1 and 2. 

When we add a substance, which is not volatile, which gives, 
however, mixed-crystals with /’, then we must take away from the 
equilibrium £ the phases F# and JZ, so that the vapour G only 
remains. Therefore, curve / must be situated in the region G. 

We may obtain also these results by using the qualitative iso- 
volumetrical and isentropical reaction, which we can deduce easily 


348 : 


from the figs 1 and 2. It follows trom the position of the curves 
in fig 1. 
towards lower 7’) towards higher 7’ 


es (21) 
(L) (G) (7) 
FU2L+G lsh So EVE *O) 
and 
towards higher P | towards lower P 
fai (22) 
(F) (@) (L) 
LOFLG AH=0 AV>0 


so that both reactions are known qualitatively. 

Now we add to this equilibrium H(2—0)= F+ L4G a sub- 
stanee, which occurs in the liquid only. As in the isovolumetrical 
reaction (21) ZL is placed at the right side of the reaction-sign, 
consequently, in accordance with our rules, T is lowered; as in the 
isentropical reaction (22) ZL is placed at the left side of the reaction- 
sign, the pressure is also lowered, therefore. 

Consequently in fig. 1 curve proceeds starting from point 7 
towards lower 7’ and P; this is in accordance with the deduced 
above, that curve / coincides with curve (Z) in this case. 

When we add a volatile substance, than it occurs in Z and G. 
As both those phases are placed in (21) at the right side of the 
reaction-sign, consequently 7’ is lowered. As Z and G are placed 
in (22) at different sides of the reaction-sign, the pressure may be 
as well increased as decreased. Therefore, curve / may be represented 
by ta or #6 in fig. 1. Which of these curves may occur in a 
definite case, cannot be deduced in this manner; we are able to do 
this, as we shall see further, with the aid of the quantitative reactions. 

In order to deduce the qualitative reactions from fig. 2, we write: 

towards lower 7'| towards higher 7’ 


3 I Sane) 
(Z) | (F) (G) 
ight (Elsa 0 AH>0 AV=0 
and 
towards higher P| towards lower P 
. (24) 
(F) (G) | (L) 
L2F+G [X16 h—"(V) LOVee=0: 


When we aid a new substance, which occurs in Z and G, then 
we find that eurve / may be represented in fig. 2 by za, 76 or te. 
It is apparent from the previous that by simple considerations 
we may deduce already something about the direction of curve # 
from the qualitative P,7-diagram of an invariant equilibrium 4(¢= 0), 


349 


When, however, we know the quantitative reactions, then we are 
able to deduce not only the quantitative P,7-diagram for the equili- 
brium E(x=0) but also (dT), and (dP), for the equilibrium L 
and consequently we can define exactly the direction of curve £. 
When we represent entropy and volume of F by H and J, of 
L by H, and JV, and of G@ by A, and V,, and when we assume 
that the substance melts on decrease of volume, then we have: 


agate oT ecridine a S80 nV <<s703- aipar(2) 
We write the isovolumetrical reaction : 
eater Ge Ong 2s We es cw. (26) 


As, in accordance with (12): 
See Orande Val Vy 4a, Vy 0) 2. (27) 

it follows: 
Vi,—V V—V, 


2 — 3 rn _ 
1 eae and 4, vieay: (28) 
so that 2, and 4, are both negative. Instead of (26) we now write: 
ieee aarGe era.) |. s (29) 
wherein 
V,—V V—V. 
———— di— Se ee Me 1!) 
; ole a 3 ae 
and 
SQ) ee Pwo A. (8D) 


Now we may prove that = (AH), is generally positive, so that, 
on addition of heat the isovolumetrical reaction (29) proceeds from 
left to right. 

In a similar way we find for the isentropical reaction : 


ny Lose? SS Go Fo oes » cee toe (GX) 
and 
2 (aAV)zp =V+u,V,—2,7, 
wherein 
HAH wi 
eT ea en uw, = may. (83) 


so that w, and mg, are both positive. 

As = (4V)z is positive, reaction (82) proceeds from left to right 
with increase of volume. 

With the aid of reactions (29) and (32), as is discussed in previous 
communications we now can deduce the P,7-diagram quantitatively ; 
then we find fig. 1. 

Now we add a new substance which oecurs in the liquid only. 


\ 


350 


When we call its concentration vw, then we have: 
= (Ax) 7 =Ave, and = (Aa) 7 ='— 8, 


so that, in accordance with (13) and (15): 


— RT 2,2, 
= ange ae) — 


Tee RT, (1%, 
= (4H) jr 


@2); = oe —- (34) 
= (AV) 
Consequently in fig. 1 curve ££ proceeds, starting from point ¢ 
towards lower P and 7’. 
It follows from (83): 
dP) ging. 2 ead eee am 
aT). 2, V4 p,V, sual, vier eee ( 
Hence it appears that in fig. 1 curve / coincides with curve (LZ). 
Also we may find (384) at once with the aid of (9) and (11). We 
put viz.: 
Sa—14+a44,=0 and Sax) =Aae, =0 
so that 2,0 and 4, = —1. Hence it follows: 
(1H) =H—H, and S(aAV)=V—Y,, 
consequently for (11) the same value as in (34). 
When the new substance occurs in liquid and vapour with the 
concentrations w, and w, then we have: 


in accordance with (29) : (02) eee 

and in accordance with (32): 2» (ae) = — we, + 4,2, 

so that (d7'), and (dP), are known again. We see that (d7’), is 
negative, but that (dP), may be as well positive as negative. Curve 


E, therefore, may be situated in fig. 1 as za or ib. 
When we put: 


ee 
u, H,—H aa 
then is 
a(n) = pb, (v= BG) 


wherein, in accordance to (35), A > 1. 
Now we find: 


a : : 
for => K is (dP), >0; consequently curve FH goes, starting 
vu, 
from point 7 towards higher pressures ; 
x 
for ~< K is (dP), <0; consequently curve EF goes, starting 
a 


from point 7 towards lower pressures. 


301 


When f.i. is K=5, then the concentration of the new substance 
in the vapour must be at least five times as large as in the liquid, 
that curve # is proceeding towards higher pressures, starting from 2. 
In order to define the direction of curve / we define the values 
of 4, and A, according (9) from: 
Pg d= 0) and) 2iai) FA 20 
(11) then passes into: 


(F)=2 Se ee (38) 
TS) a ae) a 

by which the direction of curve / is defined. This direction, as 
follows from (37), is dependent on the partition (#,:2,) of the new 
substance between gas and liquid. Also it follows from (387) that 
curve # must be situated between the curves (1) and (G). 

We now add a new substance which forms mixed-crystals with 
F, but which does not occur in the vapour. When we represent 
its concentration in / and ZL by « and 2, then it follows from (29) 
and (32): 


= (ax)y =A,a,—a2 and 2 (Ae)y = 2 — we, 


consequently : 
RT (#—a RT («—4 
eet) and (dP), = sale Hh) 


Fp se 

oe TE GH = OV)n 

It is apparent from (380) and (33) that 2,< 1 and pw, >1, but 
also that 4, differs very little only from 1. It follows from (39): 


zy 


(39) 


Curve E£ is situated then, f.i. like curve zd in fig. 1 


for », > va >A, is (dT); >90 and (dP): < 0; 
vy 


Curve £ is then situated, f.i. like curve ze in fig. 1 
for, <4, is (T)p<0 .and (dP), <0: 
«, 


Curve £ then is situated f.i. as curve 7/ in fig. 1. 
In order to define the direction of curve H we take in accordance 
with (9): 
= (a)— 1-24, — as=0 and = (Az)—-« + 1,2, —0. 
With the values of 4, and A, which follow from this we find for (11): 
(=) eines, (7, ) (2) 


aT), #,(V,—V)—2(V,—V,) ™” 


on 


352 


so that the direction of curve / is defined. 

Also it is apparent from (39) that / must be situated between 
the curves (Ff) and (ZL). 

Finally we shall assume that the new substance divides itself over 
the three phases, we eall its concentration in #2 and G aa, and 
x,. We now have according to (29) and (32): 

> (Ax)p = — a + A,r, + A,a, and = (Ax)y7 =a —p,2, + Ue, 
wherein 2, -+ 2,1 and v,=1-+4,, so that (d7), and (dP), are 
known. 

We now put: 

(te) py = cand! (tz) a ee 

As we are able to satisfy (40), independent on the values of 
r and s, by positive values of 2 v, and .a,, it follows that curve # 
may go in every direction starting from point 2. It may be situated, 
therefore, not only in one of the regions F’ and G, but also, like 
f.i. curve zg, in the region ZL. Of course its situation is dependent 
on the partition of the new substance between the three phases. 

The same considerations as for fig 1 are also valid for fig 2, for 
this we have to examine however more in detail the occurrence ot 
curve 7¢. 

Instead of (25) we have for fig 2: 

He ALS H and V, SWS Se eee) 

As }, is negative now, in accordance with (30) the isovolumetrical 
reaction passes into: 


F+1,462,,L + Ga. ey ca een AS) 
wherein: 
: V,—V as Vi—V 
_L= = and 4, = = 
Ly ep viLip 
so that 


> (1A) =2\4,— H = 1,6 
is generally positive; reaction (43) is proceeding therefore, on addi- 
tion of heat from left to right. 

When we now aid a new substance, which occurs in liquid and 
vapour, then we have:  (4x)y=2,a,—A,v,. In order that (dT); 
is positive, &(Ax)y must be negative, consequently : 

3 a 2 
Sa or = eer se oes . « (44) 

As in general V,—JV is some thousand times larger than V,— V 
curve ic therefore can, occur only in the very special case that the 
concentration of the new substance is some thousand times larger 


in the vapour than in the liquid. 


353 


We may summarize some of the previous deductions in the 
following way. 

When we add a new substance to an invariant unary equlibrium 
E(«=—0)=F+L+4G, then an equilibrium EH=F+L+G 
arises that is represented in the P,7-diagram by a curve £; this 
curve begins in the invariant point ¢ of the equilibrium EH(« = 0). 

When the new substance occurs in the liquid only, then curve £ 
coincides with curve (L) = #'+ G of the system E(x = 0). 

When the new substance is occurring in liquid and vapour then 
curve £ is situated in the region F’; its direction is defined by the 
partition of the new substance between vapour and liquid. A curve, 
like ze in fig. 2 may, however, occur only in very special 
circumstances. 

When the new substance is occurring in liquid and solid phase 
(consequently with formation of mixed crystals) then curve £ is 
situated in the region G'; its direction is defined by the partition of 
the new substance between mixed crystals and liquid. 

When the new substance occurs in the three phases, then curve 
E may be situated in each of the three regions; its direction is 
defined by the partition of the new substance between the three 
phases. 

(To be continued). 

Leiden, Lab. of Inorganic Chemistry. 


Mathematics. — ° Ueber Determinanten aus Formenkoeffizienten’’. 
3y B. L. van per Waxrrpren. (Communicated by Prof. L. E. J. 
BROUWER). 


(Communicated at the meeting of October 28, 1922). 


§ 1. Die Aufgabe. 


Vier binare Bilinearformen (av) (a’v’) bestimmen die Determinante 
Lyi lie Tea lee | 
F | 44,1 
(wo 1;, de Koeffizienten der ersten Form sind, usw.), welche inva- 
riant ist gegeniiber unabhangigen linearen Transformationen der 
beiden bindéren Gebiete « und w’, weil bei diesen Transformationen 
auch die Koeffizientenreihen linear transformiert werden. 
Sechs lineare Komplexe im dreidimensionalen Raum *# haben 
ebenso eine Invariante 
| lig ig) Lig 134 ge eo 
612 
Fiir das Problem: Derartige Invarianten symbolisch darzustellen, 
werde ich im Folgenden eine allgemeine Methode angeben und 
diese dann auf die genannten zwei Beispiele anwenden. 


§ 2. Lemma. 


Wenn eine Form f in n n-diren Vertinderlichen (eine n-dire Ver- 
dnderliche ist ein Inbegrifi von n homogenen Giréssen x, ...2%,), sich 
gegeniiber Permutation dieser Veriinderlichen verhdlt wie eine alter- 
nierende Hunktion, so enthiilt sie entweder den Klominer ine (ay 50); 
oder sie verschwindet wdentisch. 

Beweis. Setzt man zwei der Veranderlichen einander gleich, so 
verschwindet / identiseh, da dann f= — f wird. Wenn man dann 
nach dem Gleichsetzen mit Polarenprozessen operiert, so erhalt man 
immer wieder identisch Null. Also verschwindet das erste Glied der 
GorDan-CapeLii-schen Reihenentwicklung der Form fidentisch. Alle 
weiteren Glieder aber enthalten entweder den Faktor (ay...), oder 
verschwinden. Daraus folgt das Lemma. 


355 


Bemerkung. Fir den Fall (den ich eben bendtige), wo die z, y, . . . 
in / linear auftreten, ist das Lemma elementarer zu beweisen. Es 
ist dann namlich symbolisch 

ha Ay (a: ar) Oh yi pee 

Vertauscht man x, y,... in allen méglichen Weisen, und addiert 

mit +, so kommt 


| (a' x) (ay)... | 
ave (b' w) (b' y)..- P 
PUB Mon a 


oder nach dem Multiplikationssatze der Determinanten 
nmi f= A.(a db...) (2 y. «.) 


A 
a 83) el PaO) E 


§ 3. Dre allgemeine Methode. 


Es seien gegeben N Formen derselben Art, mit je N Koeffizien- 
ten. Ich setze voraus, dass man alle Invarianten vom 1. Grade in 
den Koeffizienten dieser Formen, symbolisch hingeschrieben hat. 
Verlangt wird dann, die Determinante A der N’* Koeffizienten durch 
diese Invarianten auszudriicken. Losung: Man stelle aus diesen In- 
varianten irgendeine alternierende Funktion der Koeffizientenreihen 
her. Wenn diese nicht identisch versehwindet, so stellt sie nach 
dem Lemma bis auf einen konstanten Faktor die gesuchte Deter- 
minante A dar. 

In manchen Fallen gelingt das Auffinden einer solchen alternie- 
renden Funktion sogleich. Ist dies nicht der Fall, so kann man so 
verfahren: Man wiahle irgendeine lineare Invariante / des Systems, 
und bilde 

st ME 
unter Vertauschung der Formen in allen méglichen Weisen. Es gibt 
wegen der Existenz von A sicher mindestens eine Invariante /, fiir 
welche diese Bildung nicht identisch verschwindet, und die Bildung 
stellt dann nach § 2, weil sie alterniert, bis auf einen Konstanten 
Faktor die gesuchte Invariante 4 dar. 


§ 4. Erstes Beispiel. Vier Bilinearformen in zwei unabhdngigen 
bindiren Verdinderlichen. 


Die Invarianten der Formen (12) (1'2'),..., (4x) (4'x') gehdren den 


356 


folgenden Typen an: *) 
Byy = (12) (1' 2') = Ba 
F234 = (12) (2'3') (84) (4/1!) = P3412 = F301 = Fras 
Die Invarianten vom 1. Grade in den Koeffizienten der 4 Formen 
sind also: 
Bie Bss, Bis Bos, usw. 


P4934 , usw. 
Nun ist 
= + By By =9 


es bleibt also fiir A nur die Mégligkeit: 
[Nel >>) s= Jikan 
= 44 .} F\o34— F'1934— F'1304-+ F'1423 4+ F'isa2 — P1432}. 
Zur Bestimmung der Konstanten A geniigt das Zahlenbeispiel 
OF 050 


NS") (al 


Das gibt 
1 
A= — —. 
12 
Um nun S + Fox, in seiner einfachsten Form darzustellen, ver- 
wenden wir die sich aus 
(2'3') (4’1') = (2'4”) (8'1)) + (1'2!) (8'4) 
ergebende Identitat 
F234 = — Fy243 + Bie Bsa 
Diese erlaubt uns, zwei beliebige M7. aufeinander zu reduzieren 
(durch wiederholtes Vertauschen von aufeinanderfolgenden Indizes). 
So reduzieren wir die letzten fiinf Glieder der angeschriebenen 
Entwicklung fiir 4 auf das erste. Es kommt schliesslich 


A = — 2Fj234 + Bie B34 — Biz Bea + Big Bos. 
Wenn man will, kann man auch schreiben 
A = — Fryo34 + Fogat- 


§ 5. Zweites Beispiel. Sechs lineare Kompleae tm Quaterndren. 

Geschrieben in Weirzennock—Wakgtscn’schen Komplexsymbolen?’), 
sind alle Invarianten von linearen Komplexen reduzibel auf ,,Ketten’”, 
wie 

1) Da die beiden biniiren Gebiete unabhangig transformiert werden, so bestehen 


die Invarianten aus Klammerfaktoren, deren Symbole beide demselben Gebiete 
angehoren. 

2) Siehe R. Wairzenpick, Komplex-‘Symbolik, Leipzig 1908, Wawiscu, Wiener 
3erichte Dec. 1889, oder besser den III. Abschnitt der in Kurzem bei Noordhoff 
Groningen erscheinenden ,Invariantentheorie’ von R. WEITZENBOCK,. 


357 
P22] = 2) (2) = (2)? = [2 lahisiit, adele Gb) 
[12'34'56'] = (12’) (2'3) (34') (4/5) (56’) (6'1) = [34'56'12'] = 
— [56'12'34'] — [16'54'32'] = etc. 
Die Viererkette ist reduzibel*), vermdge *) 
[12'34'] = 34 [12'] (34) — [13] [247] + 141 (231). . 8) 
Zwei Sechserketten die auseinander entstehen durch Vertauschen 


zweier aufeinanderfolgender Indizes, sind zueinander reduzibel ver- 
moge der Identitét ’) 


(2p') (p'g) (qu') + (29') (q'p) (pu') = — 3 [pg] @'y), 
zufolge welcher 
ee ye sid a eS l4’...] . . . (4) 


und dual dazu. Aus (38) und (4) folgt noch 
[12'34'56') — —[13/24'56']—1[23']{[14'][56'] —[15'][46'] 4 [16'] [45'}} 
und dual dazu (5) 
[12'34'56"] = — [21'34'56] — 4[12']{[34'][56'] —[85'][46'] +[36'] [45']} 
Um nun die Invariante 
Molise isa Zor Bl'o5 
— : 
| 612 | 
symbolisch darzustellen, bemerken wir, dass 
S + [12'] [34'] (56) =0. 
Also bleibt als einzige Méglichkeit 
AA. SE +[12'34'56']. 


Zur Bestimmung von A nehmen wir das Zallenbeispiel 


Le Oss. 
A=| 01 
und erhalten 
2 
A=—-—, 
6 
also 
2 
A=—— 2 + [1236] 2 2 2. 


Man k6énnte nun, so wie im vorigen §, diesen Ausdruck weiter 


1) Die Sechserkette ist nicht reduzibel. Vergl. R. Weritzenpéck, Jahresber. D. 
Math.-Ver. 19 (1910) und Wiener Ber. 122 (1913). 
2) R. Weirzensoéck, Invariantentheorie lll, § 5 Gl. (10). 
8) Komplex-Symb. p. 8, (26) und (26a); Invariantentheorie III, § 5 Gl. (4). 
23 
Proceedings Royal Acad. Amsterdam. Vol. XXV. 


reduzieren mittels (5); dann aber hatte man 119 Glieder zu berech- 
nen, und an jedem Gliede eine bis zehn Reduktionen yorzunehmen. 
Man weiss aber im Voraus, dass das Resultat die Form 

A = — 2 [12'34'56'] + F [[12'],.... [5692 \yauseeea 
haben muss. Wenn diese Formel gilt, so muss die duale auch gelten. 
Um A zu dualisieren, muss man 1,, durch 1',,, oder dureh 14 


B4 
ersetzen, usw.: A geht dann tiber — A. Jede Zweierkette ist zu 
sich selbst dual. Also kommt 

— A= —21'23'45'6] + F612), 15601) en) 


Subtrahiert man nun (7) und (8), so fallt die Funktion # heraus, 
und man erhalt 4 in der Form: 
A = — [12'34'56'] + [1'28'45'6)' "2 a) 
Wenn man will, kann man fiir {1’23’45’6] auch schreiben 
61’ 23'45’|, und das zweite Glied durch wiederholte Anwendung 
von (5) auf das erste reduzieren; es kommt schliesslich 


A = — 2 [12'34'56'] — Ff [12'] [34'] [56'] + [23'] [45'] [61']} 
+ gt [12)] [85'] [46°] + cyht } 
— etL14'] 123") [56] + eh} (10) 
— #tL14'] [26] [85'] + ok} 
+ @ [14)] [25'] [867] 
wo [..|{..][.-] + cyAl. bedeutet: die Summe aller Glieder, die aus 


dem angeschriebenen Gliede entstehen durch null- bis fiinf-malige 


sat eey (: Wabrend (..J[-J[-J4ek 
bedeutet: die Summe aller Glieder, die aus dem angeschriebenen 
entstehen durch null- bis zwei-malige Anwendung der Permutation 
12 34 56 

ta 56 12)- 


Anwendung der Permutation 


Chemistry. — “The dissociation constants of sulphonacetic and 
a-sulphonpropionic acids’. By Prof. H. J. Backer. (Communi- 
cated by Prof. P. van RomBuren). 


(Communicated at the meeting of September 30, 1922). 


The a-sulphoncarbonic acids are dibasic acids with a strong anda 
weak acid function. 

Consequently, the free compounds belong to the strong acids, 
whilst the acid salts behave as weak acids. 

In the table the molecular conductivity of sulphonacetic and 
a-sulphonpropionic acid is mentioned. 

When the values at an infinite dilution w,, on account of the 
number of atoms in a molecule’) are taken for the sulphonacetic 
acid at 376, and for the sulphonpropionic acid at 373, then the mean 
value of the dissociation constant, at the concentrations ‘/,, and '/,, 
Grammolecule per litre, is found to be for the sulphonacetic acid 
0.58 and for the sulphonpropionic acid 0.57. 

Great accuracy can not be ascribed to these figures, as the uncer- 
tainty in the determination of m, in the case of these strong acids 
has a great influence on the size of the constants. 

However, the values are not improbable; for Wnrascurtper’*), who 
has argued the validity of Ostwano’s dilution law for sulphonic 
acids, has calculated for benzol sulphonic, p-toluolsulphonie and 
B-naphtalinesulphonic acids, the constants 0.21, 0.214 and 0.267, 
and for the m-sulphonbenzoic acid, related to the above-mentioned 
acids, the constant 0.4. " 


In the solutions of the acid sodium salts of the sulphoncarbonic 
acids chiefly the following ionic equilibria exist: 


INREUASSONGe A. se © Q) 
W.Wess lily SU res (13) 

Besides, molecules of the free acid may be formed: 
Hie ACC Ames... . «Sct 


The conductivity of the acid sodium salts is thus caused by the 
ions: Na’, HA’, H’, A”. 
1) OstwaLp-LurHeER, Hand- u. Hilfsbuch 1922, 482. 
2) WeascHeIprR, Monatshefte f. Ch. 28, 340, 341 (1902); 30, 440 (1909). 
23* 


360 


Molecular conductivity at 25° C. in reciprocal Ohms’). 


V(Number of liters p. G. * al Oneal anes 2 64 128 | 256 | 512 1024 
Sulphonacetic acid 
C.H,O0;S 348.9 | 357.9 | 366.3 373.3 | 380.1 | 388.8 | 403.4 
Monosodium sulphonacetate 
C,H,0;SNa 88.4 | 98.4 | 110.1 | 123.9 | 141.0 | 163.2 | 191.4 
Disodium sulphonacetate 
C,H,0;SNa» 162.5 | 180.0 | 194.0 | 206.0 | 215.2 | 223.0 | 228.8 
Sulph ionic acid 
uiphonpropronic act" | 345.5 | 355.5 | 362.8 | 369.0 | 373.3 | 379.4 | 387.4 
C3H,0;S 
Monosodium 
sulphonpropionate 
C3H;0;SNa 82.6 | 91.4] 101.1 | 112.5 | 126.3 | 146.0 169.0 


Disodium sulphonpropionate 
C3H,05SNa, 154.8 | 169.3 | 182.0 | 192.6 | 201.0 | 208.0 | 213.2 


Propionanilide-z-sulphonic 
id 
CoH, O4SN 337.2 | 348.1 | 355.7 | 360.8 | 364.0 | 365.1 | 365.2 


Sodium propionanilide- 
«-Sulphonate 
CgH,90,SNNa 63.0 | 66.6 | 69.6 | 71.4] 73.3] 74.9 716.3 


In order to get an idea of the dissociation constant k, of reaction 
II, the conductivity of the acid salts must be diminished by the 
contributions of the ions Na’ and HA’. 

The conductivity of the HA-ions 444’ may, on account of the number 
of atoms, be estimated for the sulphonacetic acid at 36 and for the 
sulphonpropionie acid at 33. 

Further, the dissociation degree «, of reaction I has to be known. 

This value being not directly determinable, we may make use of 
Brepie’s rule *), that the dissociation degree of the sodium salts of 
different monobasic acids rises about equally rapidly on diluting the 
solution. 

It is therefore allowable to take the dissociation degrees sought 


‘) Only the conductivities of the neutral salts have been diminished by the 
conductivity of the water (1.5—2.0 < 10-6). 
2) Brepie, Z. f. phys. Ch. 18, 191 (1894). 


361 


as equal to the values given by the sodium salt of an analogically 
built acid in the same dilution. As the properties of the acid salts 
of the a-sulphonearbonie acids indicate the structure CHR (CO,H)SO,Na, 
the sodium salt of a sulphonic acid may be chosen for the sake of 
comparison. 


Now, with a view to determine the dissociation degree of a 
monobasic sulphonic acid, related to the acids in question, the anilide 
of sulfonpropionic acid was prepared‘). The conductivity mentioned 
in the table shows that this propionanilide-c-sulphonie acid is a strong 
acid, from which it follows with certainty, that the sulphonic acid 
group is free and that the carboxylic group is changed into amide: 
CH, . CH(CONHC,H,) . 50,H. 

If ug is assumed to be 368, a value resulting from the 
conductivity of the sodium salts and also from the number of atoms, 
then the mean dissociation constant for the dilutions 64, 128 and 
256 is found to be 0,39. 

For the sodium salt, the conductivities at the dilutions 256, 512 
and 1024, extrapolated according to Brepic, give uy = 79,0. 

From this results the ionisation degree « at the dilutions v: 


v= +P A6 32 64 128 256 512 1024 
a=0,797 0,843 0,881 0,904 0,928 0,948 0,966 


These values are also taken for a@,, the dissociation degree of 
NaHA (reaction 1). 


The conductivity of the acid salt wyaua, diminished by @,(Ana-+2 Ha), 
will give, as a first approximation, the conductivity due to the ions 
H’ and A”. 

In order to get a value for k,, it is necessary to know the con- 
ductivity which the ions H* and A” would give at a complete 
ionisation according to reaction II. 

The equivalent conductivity of the neutral sodium salts diminished 
by ana‘, gives 4,4 In this way the value 72 was found for sulphon- 
acetic acid and 65 for sulphonpropionic acid. 

The conductivity of the ions H° and A” at infinite dilution is 
then expressed by 2y + 2A ». 

The observed conductivity pnana —4@,(Ana‘ + Ana’), divided by 
this value 4y--+ 224 , gives, as a first approximation, the value 
of a,, the dissociation degree of reaction II. 


1) Recueil d. tr. ch. 40, 585 (1921). 


o- 


350 


300 


250 


— «(molecular conductivity) 


| 
He 


Now, 
tration 


a 
of 


£32 


— logv (number of litres per Grammolecule) 


| 
\- 


Eel 


362 


ESTE 
VIBE Pa 


164 1128 1256 1512 11024 


Molecular conductivity. 


Sulphonacetie acid. 
Sulphonpropionic acid. 
Propionanilide-x-sulphonic acid. 
Disodium sulphonacetate. 

Disodium sulphonpropionate. 
Monosodium sulphonacetate. 
Monosodium sulphonpropionate. 
Sodium propionanilide-x-sulphonate. 


correction may be made for the fact that the concen- 


the HA’-ions 


is smaller than agrees witb reaction I, 


363 


these ions being further split up according to reaction II. 
A corrected value for «, is obtained, from which k, may be 
calculated. 
In this way k, is found to be for the sulphonacetie acid: 
v= 16 32 64 128 256 512 1024 
ie seco tO Osa 6:0. VSO “EG Vd Se 10-5 


and for the sulphonpropionic acid: 
v= 16 32 64 128 256 512 1024 
eS O63, v0.8) 5.3) 532) 4.8: 10-5 


: 
The mean value of the second dissociation constant thus becomes 
for the sulphonacetie acid 8.9 < 10—° and for the sulphonpropionic 
acid 6.0 < 10-5. 


In this statement of views no account is taken of the combi- 
nation of the ions H” and HA’, as shown by reaction III. 

A correction for this last, however, that would somewhat increase 
the second dissociation constant is of no value for these strongly 
dissociated acids, as the uncertainty in the values of the conduetivity 
of the different ions has a greater influence. 

Dr. O. Rinecer and Drs. D. W. DisKstra have given their assistance 
with some of the measurements. 

A more detailed account will appear in the Recueil d. trav. chim. 


Organic Chemical Laboratory of the University. 


Groningen, 8» Sept. 1922. 


Physiology. — “On the progress of the veratrin-poisoning of the 
striated frog-muscle”’. By Arie Queripo. (Communicated by 
Prof. G. van RigJnBERK). 


(Communicated at the meeting of October 28, 1922.) 


1. Concentration and dose. 

The nature of the action of veratrin on the striated muscular 
tissue still has not been sufficiently revealed, partly because of the 
lack of knowledge of the conditions, associating the poisoning. 
Repeatedly we read with various authors the remark, how fickle 
and incalculable the veratrin-phenomenon is in its appearance, 
seemingly independent of the quantity of poison used and the time 
it could act. It is true in 1904 Mostinsky ') examined the factors 
cooperating in the formation of a definite shape of curve and he 
succeeded in ascertaining the conditions incidental to this; the modi- 
fications however of these conditions in the course of an experiment, 
i.e. the alterations during the poisoning of the balance between 
muscle-metabolism and poison-action of which the curve is a result, 
are unknown as yet. Closely connected with this is the question, 
in what way the shape of the curve corresponds with the rate of 
poisoning of the muscle. On this subject we have some information, 
that is two types of contraction-shape are distinguished, viz. the 
type with two and with one top (fusion type), the latter of which 
corresponds to a stronger rate of poisoning (Born ’), Denman *) ). 

In order to study these questions further, I irritated muscle- 
nerve-preparations, after their immersion in a veratrin-Ringer-solu- 
tion, by induction-shocks with so long a pause between the stimu- 
lations, that the influence of a contraction on the following need 
not be taken into account (three minutes). 

In this way I collected a great number of curves of veratrin- 
poisonings for different concentrations of the poison. On contemplating 
the modifications in the veratrinogram, we can get an idea of the 
relation between curve and rate of poisoning, for if a poisoning is 
seen to progress in the direction of a diminishing or vanishing 


1) Arch. f. exp. Path. u. Pharm., 51, 1904, 
) Idem 71, 1913: 
3) Contrib. to Biology from the Amsterdam University 1914—15. 


365 


poison-influence, proved by the final appearance of normal, single, 
rapid contractions, we see, before this stage is reached, the second 
shortening becoming lower, of a shorter duration and appearing 
after a longer latent period; conversely it follows that a strong 
poisoning will be expressed by a high, prolonged, second shortening, 
having a short latent period and that the ‘fusion type” indeed cor- 
responds with a stronger rate of poisoning than one with two tops, 
for with the former the latent period has reached its minimum, i.e. 
has grown equal to that of the first shortening; moreover the height 
is greater than that of a non-fusion second top. These magnitudes 
therefore, which may be expressed in the corresponding magnitudes 
of the first contraction, give a relative standard, holding for each 
separate muscle during the course of an experiment, for the poison- 
ing at the moment of contraction, enabling us to picture to ourselves 
the progress of the poisoning, without our being dependent on the 
direct result, viz. the shape of the curve. 

On studying the poisoning-process in this way, we notice in the 
series of curves peculiar differences, dependent on the concentrations, 
in which the poison has been applied. 

1. In concentrations of 1: 1000 and higher the muscle contracts 
as soon as it is brought into touch with the solution and maintains 
that shortening. On being stimulated the muscle shows either a very 


Fig. |. 

Experimental-process, when a veratrin-Ringer solution 1: 1000 is poured on a 
muscle-nerve-preparation. 

1: Contraction before poisoning: Af <-—>: pouring on the solution. 2: subsequent 
contraction of the muscle; 3 and 4: contraction after electric stimulation, three, 
resp. six minutes after application of the solution: at | the cylinder stopped. 
Time 1/,; sec. 


slight veratin-effect, or there is no result at all of the veratrin- 
poisoning, and the concentration is undistinguishable from the 
contraction yielded by an unpoisoned muscle on single stimulation. 


- 


366 


(Fig. 1). This reaction is soon succeeded by complete insensibility 
for stimulation. 

2. If the muscle has been put into a veratrin-solution weaker 
than 1: 1000, but stronger than 1:100000 a series of curves is 
obtained, of which either the first or a following gives the strongest 
picture of the typical veratrin-poisoning, after which this etfeet 
diminishes till it finally disappears, so that the muscle, just as before 
the poisoning, responds to the stimulation with a single, rapid 
contraction, if at least it has not become insensitive, before this 
stage has been reached. 

3. If solutions of 1: 100000 and weaker are employed, a definite 
effect of the veratrin-action is obtained, which can maintain itself 
for hours together when the preparation is regularly stimulated. 

There are three hypotheses which might explain the process 
described sub 1 and 2. 

A. When the musele has absorbed a certain quantity of poison 
and gradually diminishes the effect of this by its contractions — no 
matter how this happens — it is no more able to stand the influence 
of veratrin again. 

B. The quantity of poison in the solution is not sufficient to 
supply the quantity abolished by the muscle. 

C. In the period between two contractions the muscle modifies 
its character in such a way, that it grows less sensitive to veratrin- 
influence. 

Hypothesis A may be omitted: a muscle once poisoned by veratrin 
can very well be influenced by veratrin-action again, after the 
veratrin-effect has been abolished by repeated contracting (e.g. by 
frequent stimulation), as the experiment teaches. 

Hypothesis B may also be omitted, because von Frey’s') experi- 
ments show, that minimum quantities are already sufficient to poison 
a muscle. Therefore the hypothesis remains, that the muscle alters 
its character in the period of time between two stimulations, a 
modification which can only be attributed to the action of veratrin, 
for if all circumstances are left unchanged and only the veratrin- 
concentration is altered, a definite rate of poisoning occurs, which 
appears to be constant (third process). 

Evidently there exists, besides the veratrin-effect on the striated 
muscle, causing the well-known second shortening, another action, 
having an unfavourable influence on the effect first-mentioned, and 
causing a rapid and exhaustive effect in strong concentrations, in 


1) Sitzungsber. der Physik.-Med. Geselsch., Wurzburg, 1912. 


= 


367 


less strong ones a slow and gradual effect; while below a certain 
concentration it can no more occur. 

If the, poisoning-process in a calf-muscle, which is left in situ is 
studied here —again with a stimulation-interval of three minutes — 
the process mentioned sub 1 is never observed, because the vera- 
trin-concentration in the blood never reaches a sufficient height. 
On employing large doses (e.g. 15 mgr. per 50 Gr. frog) the heart 
is arrested after a short time as Borum') describes it and the muscle 
is in no other relation — not considering a more intensive contact 
with the veratrin-solution — than in a muscle-trough of Krirx 
Ltcas, filled with a solution of the concentration at which the 
process mentioned sub 2 occurs; the conduct of the muscle is indeed 
in absolute accordance with this. On using smaller doses (1—2 mer. 
per 50 Gr. frog), the heart, at least during the first hours after 
poisoning, keeps beating, only gradually diminishing its frequency ; 
consequently the quantity of veratrin carried to the muscle is 
steadily increased and it should be borne in mind, that when the 
veratrin-concentration exceeds a definite threshold, the second effect 
of veratrin mentioned above will make its influence felt, i.o.w. 
the poisoning will seem less intensive: conversely every contraction 
will abolish part of the veratrin-effect and it may be supposed that 
in this way interference takes place between the influence of the 
two factors, determining the effect of the rate of poisoning, viz. the 
application and the rendering inactive of veratrin, when their two 
causes, i.e. the heart-action and the lapse of time between two con- 
tractions, occur in a definite proportion. As a result of this inter- 
ference a periodicity occurs in the poisoning-process, i.e. the effects 
of stronger poisoning (higher, more prolonged second top) vary with 
those of less strong poisoning. At length the regularity of these 
oscillations is interrupted, because the heart-action diminishes under 
influence of the effect of the poison and the relation above-mentiond 
exists no more. 

A constant poisoning in a muscle in sifu can only then be obtained 
when the poison is applied without interference of the heart, e.g. 
by subeutaneous muscular injection (BucHANAN)’). 

2. Combination of veratrin and curare. 

De Borr*) communicates the possibility of leaving only the second 
shortening by simultaneous application of veratrin and curare. He 

1) Arch. f. exp. Path. u. Pharm., 71, 1913. 

*) Journ. of Physiol. 1899. 

3) Contributions Amsterdam 1914—15 and Zeitschr. f. Biol. 65. 


368 


gives few particulars however, so that I did not. think it superfluous 
to repeat this experiment. It appears that quite different processes 
may arise, dependent on the lapse of time between the application 
of the two drugs. 

A. If veratrin is first injected and the application of curare is 
put off till a distinct veratrinogram appears, the curare-injection 
remains without perceptible effect, the veratrin-poisoning proceeds 
as usual. 

b. If curare is injected either simultaneously with veratrin-or 
so short a time after, that the veratrin-effect has not yet become 
manifest in the shape of a curve, in the further course of the experiment 
a typical veratrinogram appears, which shows that the two parts 
are equally effected by curare, so that both of them diminish till 
complete indirect insensibility ; on direct stimulation the muscle even 
then gives a typical veratrinogram. 

C. If veratrin is applied, if there is already an outspoken curare- 
poisoning, no veratrin-effect is shown, the poisoning behaves as a 
common curare-action till complete indirect insensibility. 

D. \f veratrin is injected while there are slight effects of the 
curare-action — it is of course impossible to mention objective data 
on this subject — in the further progress a veratrinogram appears 
with a usually very striking second top, wich is afterwards modified 
into a normal-looking veratrinogram, which further behaves as such. 

F£. Finally veratrin may be injected between the stages C and 
D; then there arises neither a rapid contraction nor a veratrino- 
gram, but a musele-contraction, which should be identified the 
second shortening of the veratrin-curve. On direct stimulation there 
is also formed a typical veratrinogram in that case. (Fig. 2). The 
further process may lead to complete indirect insensibility, or to 
the fact that before this slow contraction there occurs a rapid one, 
causing another typical veratrinogram. In shape the shortening thus 
obtained is identical to the second contraction of a veratrinogram, 
when this succeeds the first in isolated condition, as it is sometimes 
seen during a poisoning-process. 

Examined on a quick-turning cylinder its latent period appears to 
be twice or four times as long again as that of a normal single 
contraction; no top is formed, the highest part of the contraction is 
a horizontal line; the crescent is much less steep than the decrescent ; 
the duration amounts to one to four seconds. 


3. Temperature. 
As to the influence of temperature, I agree in general with BRUNTON 


369 


and CasH*),> according to. whom both high and low temperatures 
have an unfavourable influence on the veratrin-phenomenon. 


/ 


1 2 sequin ts 1 ra SS ae 1 eee 


Fig. 2. 


Combined action of veratrin and curare; 1 and 3: contraction on indirect 
stimulation; 2: contraction on direct stimulation; period between contractions: 
three minutes; at | the cylinder stopped. Time '/, sec. 


Here too a number of details are to be observed with respect 
to the modifications, the veratrinogram undergoes at various tempe- 
ratures. 

If a frog is cooled to 4° C. or lower and a veratrin-injection 
is given after that, no poisoning-effect is observed; the muscle behaves 
as an unpoisoned, cooled muscle, giving a relatively long and low 
contraction on induction-irritation. If the frog is subsequently heated, 
the second shortening gradually appears, first rapidly and ofa short 
duration; above 14° C. the normal veratrinogram appears; conversely 
if a frog already poisoned is cooled, the second shortening disappears 
in quite the same way as it appears in the reverse experiment. 
Here too the cooled muscle behaves like an unpoisoned one. On 
heating above room-temperature the second shortening is seen to 
increase (in height as well as in duration). The first also increases 
its height as the contraction of an unpoisoned muscle would do, 
the second however increases more rapidly and consequently soon 
ecxeeds the first in size, so that a “fusion” type of curve arises. 

At about 30 degrees the second shortening still increases in size, 
now however the first grows more rapidly and at + 36° the second 
shortening begins to decrease also absolutely, the first behaves exactly 
as thecontraction of an unpoisoned muscle would do; till the musele 
has become insensitive in consequence of heat-stiffness, there is still 
some veratrin-effect left. (Fig. 3). All this oceurs quite independently 
of the poisoning: process; from every temperature with its corresponding 


1) Journ. of Physiol. 1883. 


370 


curve-shape, we can return to room-temperature and see a typical 
veratrinogram arise. 


s oC 6°C 
te te aif 
SS 4 on 


et kk eee el 
IPSC, 
pameenerpeweyee rs 
Voor afkoeling = Before cooling. 


Shapes of veratrinogram, yielded by one muscle at various temperatures. Time 
1/, sec. 


4. Strength of stimulus. 

I have not succeeded in exercising an influence on one of the 
two parts of the veratrinogram separately by means of the strength 
of the stimulus. If the strength of the stimulus is gradually diminished, 
we may observe as Mostinsky') describes, the critical progress of 
the excitability of the veratrin-muscle, i.e. below a definite limit, 
which is very exact, no reaction occurs on irritation, above this 
limit a reaction, differing but little from the maximal; moreover 
this always is a complete veratrinogram. 

»A more detailed research concerning the problem of veratrin 
will appear in the ,,Archives de Physiologie Neéerl.”” 


1) loc. cit. 


Anatomy. — “The Problem of Orthognathism’. By Prof. L. Boix. 


(Communicated at the meeting of October 28, 1922). 


In the meeting of February 1921 I called attention to the fact 
that the typically somatic human features are of a special character, 
viz, they are persisting fetal properties and conditions. | referred 
this fact to the influence of the endoecrin system, which, through its 
inhibitive action, fixes fetal morphogenetic relations. The character 
of the human body, therefore, is its fetality, and this character 
results from what | am inclined to term a process of fetalization. 

When studying the structure of the human skull from this point 
of view, it is surprising to note how all at once the whole complex 
of the typically human features, — and there are many in the skull 
— becomes easy of comprehension. Of all parts of the human body 
the head is most indicative of its fetal character. Earlier researches 
made by me had already favoured this view with regard to several 
of these properties. Long before conception of the fetalization-prin- 
ciple as the leading factor in the genesis of the human body as a 
whole, I had already pointed out that many somatic property 
of man represents an early stage of ontogenetic development. 

However, there was one property of the skull about which I had 
no fixed opinion, and it is just this property that determines so 
emphatically the human physiognomy viz. its orthognathism. The 
question urged itself upon me, whether also this feature should be 
a persisting fetal property? I felt some diffidence in putting the 
question, as the pronouncements laid down in the literature were 
not very encouraging, the general conception being that the ortho- 
gnathous (i.e. the human) skull-type has originated from the pro- 
gnathous (i.e. the animal) type. The evolution is supposed to have 
consisted in a shortening of the jaws, in connection with the 
presumed reduction of the set of teeth. Now, to this conception 
objections might be raised also from other quarters, but | deemed 
it necessary, instead of opposing one speculation to another, to let 
the facts speak for themselves. This led me to an inquiry into the 
relation between prognathism and orthognathism. The results were 
indeed surprising, for not only was I in a@ position to establish this 
relation, but it also became evident that the whole complex of 


372 


luman properties’ in the skull form one entity. However, in this 
paper I shall confine myself to my real subject. 

My first attempt was to ascertain the essential morphological fea- 
tures of the prognathous and the orthognathous skull-type, for the 
criterion of short or long jaws is inadequate. With the aid of Figs 
1 and 2 these features are easy to establish. 


Fig. 2. 


Fig. 1 shows a median section of a human skull. Fig 2 asimilar 
section of the skull of Lemur, a Prosimia. Three lines have been 
drawn in both figures, viz the axis of the cranial cavity, the axis of 
the nasal cavity and the axis of the base of the skull. The three 
lines demonstrate in a simple way the essential features of the 
orthognathous and the prognathous skull-ty pe. They are the following: 
In the orthognathous type the axis of the nasal cavity is approxi- 
mately perpendicular to the axis of the cranial cavity, in other 
words the nasal cavity is situated beneath the cranial cavity; in 
the prognathous type, on the contrary, the axis extends more or less 
in the same direction as the axis of the cranial cavity. As to the 
axis of the base of the skull, it is flexed in either case, but in 
opposite direction. In the orthognathous type it is flexed between 
the basi- and the praesphenoid, an angle is formed with its open 
side turned anteriorly downwards. It is known in the literature as 
the sphenoidal angle. In the prognathous type the base is flexed 
between the praesphenoid and the ethmoid. An angle is formed with 
its open side turned posteriorly upwards. This angle I shall term 
the ethmoidal angle. 

So it appears that the typical differences between the orthognathous 
and the prognathous skulls consist in the different situation of the 
nasal-cavity, either subcerebral or praecerebral, and in the different 
direction in which the base of the skull is flexed. The length of 
the jaws | do not consider as a fit criterion. 


———— 


373 


Now, when we test the skulls of the various classes of mammals 
by the criteria just mentioned, it appears that the whole class of 
the Primates, so not only man, is characterized by an orthognathous 
skull, in contradistinction to all the other mammalian classes. Applying 
the degree of prominence of the jaws as a criterion for prognathism 
is an erroneous method, which e.g. has led to the classification of 
apes among the prognathous forms. Though their jaws may be ever 
so much developed, the base of the skull never presents an ethmoidal 
angle, while the nasal cavity is never situated before the cranial 
cavity and in younger individuals there is even a sphenoidal angle. 
The strongly developed facial part of.the skull in several apes, 
however, reminds us forcibly of a prognathous skull. These forms 
I will, therefore, distinguish as pseudoprognathous. 

In the foregoing the principle has been established for an inquiry 
into the relation between prognathism and orthognathism. The 
object of such an inquiry must be the answer to the question: 
which skull-type is the primitive one and which is the specialized 
type. First of all [ will report the result of my examination of 
embryos of a number of mammals. It is the following: the fetus 
of all mammals is initially orthognathous, i.e. has a sphenoidal angle 
lacks an ethmoidal angle and the nasal cavity is subcerebral. Now, 
whereas this condition persists in apes partly and in man completely, 
in the other mammals the fetal orthognathous skull passes gradually 
into the prognathous type; first the sphenoidal angle disappears, 
then the ethmoidal angle is developed and coincidently the nasal 
cavity rotates; its subcerebral position passes into a precerebral 
position. So it becomes evident that the orthognathous condition in 
man, which is the special feature of the human physiognomy, reveals 
itself again as a persisting fetal property. 

Before demonstrating this in a series of embryos, I will briefly 
dwell on the fact that this transformation of the orthognathous skull 
into the prognathous type is a process, with which we are confronted 
already in Reptiles, so that it has evidently been inherited by the 
Mammals from their reptilian ancestors. 

Fig. 3 represents a median section through the head of an eurbryo 
of Lacerta, length of the head 4 mm. The chorda is still present, 
the vertebrae are not differentiated, likewise the cranio-vertebral 
joint is still incomplete. Of the chondrocranium the basicranial plate 
enclosing the Foramen can be recognized. This plate extends frontad 
as far as the Hypophysis cerebri, which is still attached to the 
epithelium of the roof of the mouth. In front of the Hypophysis lies 
the prechordal plate. The latter presents two enlargements the one 

24 

Proceedings Royal Acad. Amsterdam. Vol. XXV. 


374 


turned upwards: the septum orbitale, and the other turned down: 
the septum nasale. 


Fig. 3. Fig. 4. 


Now, two things should be observed: First that the prechordal plate 
extending in front of the Hy pophysis,forms an angle with the basicranial 
plate behind it. This angle which is still more distinet in younger 
embryos, is identical with the sphenoida angle, the typical feature of the 
orthognathous human skull. The second thing to be observed is the 
direction of the septum nasale. In this young Lacerta embryo the 
axis of this septum is perpendicular to the base of the skull, whieh 
also is a typical feature of the orthognathous human skull. In pas- 
sing, [ wish to point out that in this phase of developmeut the 
entrance to the mouth is, in Lacerta, not apical, but points down- 
ward. This reminds us incontinently of the permanent condition in 
Plagiostomes. 

So the verticality of the septum nasale is a characteristic which, in 
this phase of development, the head of the Lacerta-embryo has in 
common with the orthognathous type. Fig. 4 shows how this type 
passes into the prognathous. In fig. 4¢ the median section through 
a primordial cranium is given, head length 4.5 mm. In fig. 4° 
the same with a length of 5 mm.; the enlargement in the two 
figures differs. Relative to the younger stage, the septum orbitale 
in the embryo with a head length of 4.5 mm. is considerably enlarged. 
It is clear that the axis of the nasal septum is no longer perpen- 
dicular to the base of the skull, but has rotated anteriorly. In the 
5 mm. embryo this rotation is so considerable that the axis of the 
septum nasale is nearly on a level with the base of the skull. In 
this older embryo the septum orbitale exhibits marked signs of 


375 


resorption. So the figares 3 and 4 illustrate a rotation of the septum 
nasale, and consequently of the facial skull. From its original sub- 
cerebral position (orthognathism) it shifts into a precerebral position 
(prognathism). That in connection with this rotation plagiostomy 
changes into teleostomy we will pass over in silence, although this 
phenomenon would give ample scope for interesting observations. 

It has thus been shown that the chondrocranium of Reptiles, in 
its early phase of development, resembles the orthognathous type. 
Now we are going to demonstrate that the process of development 
in Mammals bears a great resemblance to that of Reptiles. | have 
studied the ontogenesis of the skulls of a number of Mammals, and 
in all of them I met with the phenomena that I am going to 
describe for the skull of Mus decumanus. 

Fig. 5 represents the median section of an embryo of Mus 
decumanus of 11.5 mm. In this stage the primordial cranium is 


sufficiently differentiated. We will confine ourselves to the skeleton, 
omitting all further remarks that the following series of figures might 
suggest. In this stage the Hypophysis has become a closed vesicle, 
which, however, still adheres to the epithelium of the mouth. Behind 
the Hypophysis lies the basicranial plate, which in Mus is subchordal 
over its whole length. Frontal to the Hypophysis lie the prechordal 


plate presenting a slight broadening dorsad, which is homologous 
with the strongly developed Septum orbitale in Reptiles. At its lower 
surface the Septum nasale is fastened. There is no denying that the 
basicranial plate and the prechordal plate form an angle. This 


angle, which we also found in Lacerta, is the sphenoidal angle that 
we know to be the typical feature of the orthognathous skull. Whereas 
the base of the skull is directed almost quite horizontally, the axis 
of the septum nasale is directed perpendicularly. Therefore in 
this stage of development the nasal cavity of Mus is subjacent to 
the cranial cavity. The skull of this young embryo of Mus possesses, 
therefore, two features, which are characteristic of the orthognathous 
skull, viz. a sphenoidal angle and a subbasal situation of the nasal 
cavity. That the latter condition is not the consequence of the intense 
development of the cerebral hemispheres, is borne out by the fact 
that in an early stage of development of Reptiles we find the same 
direction of the septum nasale. The condition in Mus, just deseribed, 
is inherited from the reptilian ancestors of Mammals, whieh in 
their turn have inherited it from more primitive vertebrates. Plagio- 
stomy, to which we referred heretofore, and which, to some extent, 
is encountered in the represented embryo of Mus, indicates in what 
direction we have to look for an explanation of this condition. 

Accordingly we conclude that orthognathism is the characteristic 
of the young fetal mammalian skull. Now let us see how the prog- 
nathous type is developed from the primitive type. 

Fig. 6 illustrates the median section through the head of an embryo 
of 13.5 mm. in length. The chorda begins to disappear, the Hypo- 
physis lies within the cranial cavity, but is still attached to the 
mouth-epithelium. The base of the chondrocranium begins to stretch, 
but the sphenoidal angle is still recognizable. The axis of the septum 
nasale is still perpendicular to the prechordal plate. 


Fig. 7. Fig. 8. 
Fig. 7. Embryo of 20 mm. The basis cranii is stretched, the 


677 


sphenoidal angle has disappeared. The axis of the nasal septum is 
no longer vertical to the base of the skull, it has rotated, so that 
it forms an angle of 115° with the axis of the base of the skull. 

Fig. 8. Embryo of 25 mm. The canalis Hypophyseos is closed, 
basal plate and prechordal plate have coalesced completely. The 
septum nasale has rotated further, and is inclined to the base of 
the skull at an angle of 130°, the part of this base to which the 
septum nasale. is attached is bent slightly upwards, which is the 
first indication of the developing ethmoidal angle. 


Fig. 10. 


Fig. 9. Embryo of 35 mm. Three centra of ossification have 
appeared in the basis. cranii' for the Basioccipitale, the Basisphenoid 


378 


and the Alisphenoid. The rotation of the septum nasale has conti- 
nued; the nasal cavity now lies obliquely under and anteriorly to 
the cavum eranii. This rotatory movement apparently results from 
the further upward flexing of the frontal part of the basis cranii. 
The ethmoidal angle now becomes distinctly visible, right in front 
of the centrum of ossification of the Alisphenoid. 

Fig. 10. Embryo of 43 mm. The ethmoidal angle has reached 
its definite value for the skull of the adult rat, the frontal part of 
the basis cranii has now become the anterior wall of the cranial 
cavity, the nasal cavity is situated before the cranial cavity, the 
skull has become prognathous. 

It is evident, then, that the transformation from the orthognathous 
into the prognathous skull-type in the mammalian embryos is a 
regular process in which two sueceeding phases are recognizable. 
In the first phase a straightening of the basis cranii takes place; 
the sphenoidal angle disappears. Its disappearance it attended with 
a change in the direction of the septum nasale, which is now placed 
obliquely to the base of the skull. After this the second fundamental 
alteration in the basis cranii commences, viz. the formation of the 
ethmoidal angle, the anterior (ethmoidal) portion of the base being 
turned up together with the septum nasale, which is attached to it. 
Consequently a part of the base of the fetal skull becomes the front 
wall of the cranial cavity. 

I shall not enter into details concerning the various mammalian 
embryos that I have examined but will only add a few general 
remarks. 

From the foregoing it is sufficiently evident that the orthognathous 
skull of man is to be considered as a persisting early fetal form. 
In stating this fact we have at the same time disproved the current 
opinion, that the sphenoidal angle, which is so characteristic of the 
human skull, is due to the inteuse development of the human brain. 
This angle, indeed, is not only a feature of all fetal mammalian 
skulls, but it oceurs even in the chondrocranium of Reptiles. It is 
an essential character of, let me say, the primordial cranium of 
vertebrates in general. I shall not discuss this point any further. 

The question now arises whether the intense growth of the 
Hemispheres has had no influence whatever on the anatomical relations 
of the skull, apart from the necessarily considerable enlargement of 
the cerebral crane. Such an influence, and even a very remarkable 
one, can indeed be demonstrated, as may be seen in comparing 
Fig. 11 and 12. 

Fig. 11 shows the median section through the head of a dog’s 


379 


fetus; length 32 mm.; Fig. 12 that of a human fetus 40 mm. long. 
The peculiarity I wish to lay stress on, regards the insertion of the 


Fig. 11. Fig. 12. 
membranous vanlt of the crane on the cartilagenous nasal capsule. 
In the dog the former attaches itself to the acute border where the 
cranial base bends round in the nasal capsule, i.e. to the anterior 
margin of the cranial base. In man, on the other hand, it attaches 
itself in consequence of the intense development of the Hemispheres, 
to the anterior surface of the nasal capsule. It is obvious that a 
comparatively large portion of the nasal septum is hereby enclosed 
in the cranial cavity. This fact elucidates several phenomena observable 
at the human skull, I will only name them parenthetically. The 
shifting of the insertion of the membranous cranium to the anterior 
surface of the cartilagenous nasal capsule accounts for the occurrence 
of the Crista galli. This process, which is lacking in prognathous 
skulls is merely the top part of the nasal septum and the apex of 
the Crista galli indicates consequently the original frontal boundary 
of the base of the skull. This transference of the insertion of the 
membranous vault causes a shoriening of the frontal part of the 
nasal region in man and it is quite obvious that the human physi- 
ognomy has been largely influenced by it. Harlier comparative 
anatomical inquiries already led me to conclude that the top part 
of the nose in Primates was reduced, and that the present boundary 
between nose and vault of the skull is of asecondary nature’). The 


1) Die Herkunft der Fontanella metopica beim Menschen. Anat. Anz. Erginzungs- 
heft. Bnd 38. Jena 1911. 


380 


suture between nasal and frontal bones was lying on the forehead 
at the spot where in man not seldom the so-called Fonticulus 
metopicus is situated. The results of the embryological research lend 
support to this view. 

Another phenomenon explained by this transference of the insertion 
of the membranous vault on the nasal capsule is the intra-orbital 
situation of the entrance to the lacrimal duct. In the half-apes this 
Opening is extra-orbital; in the apes, on the other hand, it is taken 
up in the medial wall of the orbit together with the os lacrymale, 
in consequence of the shortening of the facial part of the skull in 
this region. 

It appears then that through this transference of the insertion 
of the membranous vault to the anterior surface of the nasal capsule 
in consequence of the intense development of the cerebral hemis- 
pheres, we are able to interpret in a simple way three apparently 
heterogeneous phenomena, viz. Crista galli, Fonticulus metopicus, 
and intraorbital position of the lacrimal foramen. In this connection 
I may still add a remark about the other Primates. We have stated 
that apes, however much their jaws may project, possess in reality 
an orthognathous skull like that of man; they are to be classed as 
pseudoprognathous. The persistence of the subcerebral position of 
the nasal cavity, also in apes, is the reason why the human 
physiognomy is ever more or Jess discernible in apes, which is to 
be aseribed chiefly to the position of the eyes. Originally the eyes 
of all mammalian embryos are disposed on the lateral surface of 
the head. In the prognathous type, in which the nasal cavity rotates 
before the cranial cavity the eyes retain their lateral position. In 
the orthognathous type, on the contrary, in which the nasal cavity 
persists under the cranial cavity the eyes can draw nearer to each 
other, and instead of the nasal cavity the orbitae occupy a precerebral 
position. Now this rotation obtains with all Primates, and this is 
why, pbysiognomically, apes resemble man. 

In conclusion another point of similarity is the fact that all 
Primates possess a Crista galli, so in all of them the insertion of 
the membranous vault of the crane is transferred to the nasal capsule 
under the influence of the intense growth of the cerebral hemispheres, 
which is proved also by the intraorbital position of the foramen 
lacrymale in .this class of mammals. : 


a 


381 
ERRATUM. 


In these Proceedings Vol. XXV n°’. 5 and 6, p. 202, line 15 
from the bottom, to replace “with respect to time” by “with respect 
{0 TEMPERATURE’. fe 


\ 


a} 
Gi 


Yeswari Svbor* yd “ans of Sosqae: Aten? essigos oF (mnanod 


. 7 3 - 
4 186 5 
. MUTAAAN : 


anil S08 a) 8 hus 6 n VEX fot agnibassord 


. a 


1s 


7 _ 
be 
he 
7 ry iad 
- id 


KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN 
TE AMSTERDAM. 


PROCEEDINGS 


VOLUME XXV 
Nes, 9 and 10. 


President: Prof. F. A. F. C. WENT. 
Secretary: Prof. L. BOLK. 


(Translated from: "“Verslag van de gewone vergaderingen der Wis- en 
Natuurkundige Afdeeling,” Vol. XXXI). 


CONTENTS. 


J. P. KUENEN +: “The Magneto-Thermic Effect according to Thermodynamics”, p. 384. 

SHINKICHI HORIBA: “Determination of the Vapour Pressure of Metallic Arsenic”. (Communicated 
by Prof. P. ZEEMAN), p. 387. 

B. SJOLLEMA: “On the Influence of the Composition of the Food on the Calcium output”. (Commu- 
nicated by Prof. H. ZWAARDEMAKER), p. 395. 

J. J. VAN LAAR: “On Heats of Mixing of Normal and Associating Liquids”. (Communicated by Prof. 
H. A. LORENTZ), p. 399. 

H. A LORENTZ: “On WHITTAKER’s Quantum mechanism in the atom”, p. 414. 

E. D. WIERSMA: ,Concordance of the Laws of some Psychological and Physiological Phenomena”, 
p. 423. 

G. HERTZ: “On the Separation of Gas Mixtures by Diffusion in a Flowing Gas’. (Communicated by 
Prof. P. EHRENFEST), p. 434. 

G. HERTZ: “On the Excitation and Ionization Potentials of Neon and Argon”. (Appendix). (Commu- 
nicated by Prof. P. EHRENFEST), p. 442. 

H. KAMERLINGH ONNES and W. TUYN: “Further experiments with liquid helium. Q. On the electric 
resistance of pure metals etc. X. Measurements concerning the electric resistance of thallium 
in the temperature field of liquid helium”, p. 443. 

H. KAMERLINGH ONNES and W. ‘l'UYN: “Further experiments with liquid helium. R. On the electric 
resistance of pure metals etc. XI. Measurements concerning the electric resistance of ordinary 
lead and of uranium lead below 14° K.", p. 451. 

J. P. WIBAUT and ELISABETH DINGEMANSE: “The Action of Sodiumamide on Pyridine, and some 
Properties of <-aminopyridine”. (Communicated by Prof. A. F. HOLLEMAN), p. 458. 


L. HAMBURGER: “On Centres of Luminescence and Variations of the Gas Pressure in Spectrum 
Tubes at Electrical Discharges”. I1 (Communicated by Prof. H. A. LORENTZ), p. 463. 

F. A. F. C. WENT: “On a new clinostat after DE BOUTER”, p. 475. 

B. SJOLLEMA and J. E. VAN DER ZANDE: “Concerning the Synthetic Action of Bacteria in the 


Paunch of the Cow”. (Communicated by Prof. H. ZWAARDEMAKER), p. 482. 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


Physics. — “Vhe Magneto-Thermic Effect according to Thermo- 
dynamics’. (Supplement N°’. 47 to the Communications from 
the Physical Laboratory at Leiden). By Prof. J. P. Kurnen f. 


(Communicated at the meeting of December 30, 1922). 


In experiments with ferro-magnetic substances Wuiss and PiccarD *) 
found that the heat-effeet which accompanies a magnetic change, 
assumes a relatively large value in the neighbourhood of the Curie- 
point. Aecording to them this phenomenon, just as the discontinuity 
in the specific heat at the Curie-point?), is a consequence of the 
“molecular field’, which plays a prominent role in Weiss’ theory 
of ferro-magnetism. 

It is natural to apply equations to this phenomenon which ensue 
from the second law of the theory of heat. The question suggests itself 
whether this is allowed, as non-reversible changes oceur in ferro- 
magnetism. Every condition — leaving disturbances out of account 
— is indeed a condition of stable equilibrium, but in general the 
substance cannot pass through a definite series in both directions. 
This difficulty may be obviated by considering only those condi- 
tions that arise under the influence of strong mechanic or electric 
vibrations: these neutralize hysteresis, and with it also remanent 
magnetism, and the conditions then become reversible. The results 
obtained by the aid of thermodynamics, will in main lines most 
likely also hold for the phenomena occurring under normal cireum- 
stances: above the Curie-point they are, of course, strictly valid. 

The external work of a magnetized system being represented by 
—Hdo, where H and 6 denote resp. the magnetic force and the 
magnetisation, the chief equation of thermodynamics is: 


de— T dy Hdo7 (ee a0) 


As it is most convenient if H/ is an independent variable, we 
write: 
d(¢ — Ho) =Tdy—6046 Haine eee) 
from which follows: 


1) P. Weiss et A. Piccarp, J. de Phys. (4) 7, p. 103, 1917. 
2) P. Weiss, A. Piccarp et A. Caprera, Arch. de Genéve 1917; J. de Phys. 
(Sy 7e yas tev alent 


385 


oT 00 T 06 
eS SS = SS Se, 8) 

0H, O77 C7 One 
Here c, is the specific beat for constant field. This equation 
shows that the thermic effect in question is greatly dependent on 


00 


Te hence becomes abnormally bigh in the neigbourhood of the 
H 


Curie-point, and this is what we intended to prove. 

o being <0, the temperature increases during the magnetisa- 
tion, and reversely. According to the above-mentioned experiments 
e¢ would suddenly assume a lower value at the passing of the 
Curie-point in upward direction, but this does not affect the con- 
clusion drawn. The relation found is independent of Weiss’ hypo- 
theses, and sets forth the inter-relation between heat-effect and 
disappearance of ferro-magnetism more clearly than the equations 
given by Weiss and Piccarp. 

When, with Weiss and Piccarp, o is taken as independent vari- 
able, the following is found from (1): 

GH OH.» T 0H 
Uy aliens /-. . is Co 


6 2 
Above the Curie-point = (T—6) = C, where 6 and C are con- 


o 
stants, so that re On substitution of this in (4) an equation 


is obtained which also occurs in the cited paper, but which is 
strictly proved here without having recourse to Wuiss’ special theory. 

It will be vainly tried to estimate the said change of the specific 
heat at the Curie-point purely thermodynamically. Thermodynamics 
gives, indeed, the change of cq with the value of H (resp. of 
c; with o), and the difference between c,, and c., but not the 
dependence on the temperature in question. To find this a molecular 
theory like that of Weiss, is indispensable. From this an expression 
for the internal energy ¢ will have to be derived, and also for the 

de do 


é 
c’s, because c; = —— andc, = — = —- 
? or A OD Oly 


In connection with the preceding paper I may be allowed to add 
a few remarks. 
The late Professor Kurnen had the intention to make a commu- 
nication on the subject mentioned in the title at the Meeting of the 
25* 


386 


Royal Academy of Sept. 30 1922; a few days, however, before the 
meeting death took him away. Among the papers found after his 
death was the manuscript of the above communication, ready 
for the press, and a few detached sheets, on which the author tried 
to ascertain what follows from the equations : 

do \? 

(er) 


Gy, == 6g PS Oe ee eC) 


00 
(sa), 


(0 
oy ACC 7a = 


Oc, (6 
@E Ga), 2, fe Si eee) 
0 (¢y\|__ (0n do \? (0n vo \ 
Ei Glace Gur oe (sm) = 
(=m) - (D) 
_ (9% OG VE VG Oy aa 
(a ).(ar) 


~ \de2 oT) T (06 
are 


which can be derived in a purely thermodynamic way, if they 
are combined with the empirical data on the course of 6 = g (7, H) 
in the neighbourhood of the Curie-point, or with the equation: 


nO 6 
Se armed a He kos ot (2) 


which is the direct consequence of the formula for the molecular 
field H,, used by Prof. Weiss: 
Hy= —(55) no jk seeh | sit) Se RIE RL ELD) 
00/7 
It seems to have been his intention to throw light on the question 
what suppositions are necessary to derive the change of the specific 


heat of ferro-magnetic bodies at the Curie-point. 
ep 


Chemistry. — ‘Determination of the Vapour Pressure of Metallic 
Arsenic”. By Suinkicut Horrpa. (Communicated by Prof. 
P. Zeeman). 


(Communicated at the meeting of October 28, 1922). 


Arsenic is one of the most interesting elements, which should be 
studied from the view-point of the theory of allotropy. It is a well 
known fact that arsenic can exist in three kinds of modification, i. e. 
gray, black, and yellow; the gray modification is quite stable in a 
wide range of temperature, while the others are rather metastable. 
Although many investigations have been carried out about this 
important element, yet it has never been tried to define the exact 
lines of demarcation between these three modifications. Recently 
some observations of its melting point have been reported by GouBrav’), 
Heikr *), Rassow*), and some measurements of the vapour pressure of 
its solid phase by Heike, but in the ease of the latter, an indirect 
method was used, so that the results were not very accurate. The 
vapour pressure of the liquid phase of this element has never been 
determined. On the suggestion of Professor Smits, the author has 
undertaken the measurements of the vapour pressure of this element 
in the laboratory of the University of Amsterdam ; the object of 
the present study is, of course, to investigate the whole system of 
this element, but the author is not yet in the position to complete 
this study, owing to the difficulties of the technics of the measure- 
ments. The present communication will only represent the results 
of the measurements of the vapour pressure of the gray modification 
and give some thermal data which can be calculated from these 
vapour pressure data. 


The Method of Investigation. 

The same method of investigation, used by Prof. Smirsand Bokuorst *) 
for the study of phosphorus, was applied; a small modification, 
which was made in the present investigation, was that a quartz 
indicator of pressure was used instead of the hard glass, in view 


1) Compt. rend., 152, 1767, (1911). 

*) Z. anorg. chem., 117, 147 (1921): the literature of the melting point was 
given in this paper. 

3) Z. anorg. chem., 114, 131 (1920). 

4) Z. physik. chem., 91, 249 (1916). 


388 


of the high melting point of arsenic. Owing to the technical dif- 
ficulties of making such an indicator, its sensibility was some- 
what inferior to that of the indicator made of glass, still some of 
the indicators which were used, could keep their sensibilities within 
one centimeter of mercury, being sufficient for the present purpose. 


The Material. 

Merck’s metallic arsenic was used after several purifications. At 
first the finely powdered sample was subjected to repeated subli- 
mation in a vacuum by the aid of a large Heraeus electric furnace, 
the temperature of the furnace was maintained at a little over 
500° C. in the first sublimation and at nearly 600° C. in the final 
one. The gray modification thus prepared was again very finely 
powdered, and was extracted by carbon disulphide in a Soxlet appa- 
ratus for 24 hours. A small quantity of arsenic oxide, which would 
still remain in the above purified sample, must be reduced by 
hydrogen current in the pressure indicator itself. 


The Filling of the Sample in the Pressure Indicator. 

About 10 gr. of the sample was placed into thé bulb of a quartz 
indicator, and a hard glass capillary tube was introduced into the 
bulb of the indicator, so that the end of the capillary tube was just 
in the spring of the indicator. Then the indicator was heated from 
outside by Bunsen burners at 500° C; during the heating of the 
indicator a current of purified hydrogen was passed into the bulb 
and its spring through the above mentioned capillary tube, so that 
a small quantity of arsenic oxide, which still remained in the sample, 
was at first sublimated and the rest of it reduced to pure arsenic. 
After a sufficient sublimation in this way, the remainder of the 
sample in the bulb became perfectly pure brilliant metallic arsenic. 
Then the indicator was completely evacuated and the bulb of it 
was sealed up. It was always observed that if arsenic was sublimated 
in a vacuum, even at room temperature,’ at first it appeared as the 
yellow modification, which would be soon transformed into the black 
modification. . 


The Furnace of the Pressure Measurement. 

A special furnace was constructed for the purpose of keeping the 
indicator at constant temperature, even at very high temperature. 
A large iron block of 14 em. in diameter and of 30 ecm. in height 
was heated electrically by nichrom wire. In the middle of this iron 
block, a hole of 3 em. in diameter and of 25 em. in depth was 


389 


bored, in which the indicator and a thermoelement were placed. 
This furnace was available till 900°. The temperature of the furnace 
was measured by a Heraxus platinum-rhodium thermoelement, which 
was carefully adjusted before the experiment. 


The Measurement of the Vapour Pressure. 
The method of the pressure measnrement by an indicator is exactly 
the same as that applied by Prof. Smits and Bokuorst '). The equi- 


TABLE I. Vapour Pressure of the Solid Phase. 


— = 7351 C = 8.219 
t patm. (obs.) Tlogp | pi | A ) | PD (calc.) 
450 0.026 | — 1142 7127 == 230 0.013 
500 — 0.076 — 844 7244 Silk) 0.075 
525 0.105 — 620 7227 — 130 0.094 
550 0.222 — 538 7352 +5 0.219 
568 0.362 = yf 1334 E25 0.340 
592 0.584 — 202 7363 + 6 0.598 
604 0.785 92 7353 =a 0.777 
615.5 0.997 = 7357 +0 0.997 
631 1.395 131 71354 =, 5} 1.387 
658 2.392 353 7354 = %) 2.377 
665 oT | 401 7305 es 2.729 
672 3.035 456 7371 + 20 3.189 
685 3.906 567 1365 15 S19! 3-983 
697 4.85 664 7368 aeeait 4.96 
720.5 6.95 838 7386 2g 1.46 
741 9.7 999 7396 + 39 10.6 
758 13.3 1157 7378 42a | 1420 
712 16.9 1281 7371 + 14 17.4 
790 22.3 1432 7368 SL (ites) pire 
801 26.1 1522 7370 se 4g 26.9 
809 30.0 1595 1363 + 6 | 30.2 
815 33.6 1662 7348 =n 33.0 


1) loc. cit. 


390 


TABLE II. Vapour Pressure of the Liquid Phase. 


Q_ — 2450 = 3.80 
4.571 Oe 
| SCG) 

t | patm. (obs.) | Tlogp | 4.571 Ops p (calc.) 
808 34.2 1658 2450 +0 34.2 
817 Bei 1693 2453 + 3 35.9 
830 38.1 1743 2448 —2 38.0 
843 40.5 1793 2447 — 3 40.2 
850 41.6 1818 2449 —1 41.5 
853 42.2 1829 2450 +0 42.2 


librium between vapour and condensed phase of arsenic is not very 
quickly established but the heating of the furnace was so slow 
that there was no difficulty to measure the pressure at any desired 
temperature. The whole measurement of the vapour pressure of the 
gray modification of arsenic to its liquid phase, namely from 400° C. 
to 850° C., required a continuous work of more than 12 hours. The 
results of the vapour pressure measurement were tabulated as follows : 
(See Table I, page 389). 

Starting from Cravsius and CLApayron’s equation and assuming that 
the heat of vaporization Q, is constant, that the vapour of arsenic 
follows the gas law and that the volume of the condensed phase 
can be neglected with respect to that of the vapour, the vapour pressure 
would be represented by a straight line 7’ log p= — Se Gall 

When the value of 7’ log p, from the observed values of pressure, 
was plotted against temperature, a good straight line was obtained 
from 550° C. to 700° C. as shown in Fig. II, from which we can 
easily calculate Q/4.571 and C. The table contains in the last column the 
values of the pressures calculated from this equation. Above 700° C. 
however, the 7 log p—t curve shows some deviation, and the calculated 
values of Q/4.571, assuming C as a constant must deviate. The deviations 
become gradually smaller as the temperature rises. Some of these 
deviations may, of course, be experimental errors, because at high 
temperature a little observation error of temperature wonld have a 
great effect on the value of pressure, quite the contrary of the case 
at low temperature, where a little error in the measurement of 
pressure, owing to small value of pressure, would have a great 
effect upon the calculated value of Q/4.571. But such a deviation 


391 


as observed here depends certainly on the inapplicability of the 
assumptions which were used in the integration of the CLaustus— 
CLAPAYRON equation. 

In the case of the liquid phase, the observed vapour pressures 


a eg fs 
50 
il 
| | 
40 a IL | 
«3 
p | 
= | 
Z 30 | 
=| if 
= | 
zz | 
2 20 
é 
10. i = 
0. pee 
rr) SSS = oe ee 5 = ° 
400) 500 600 700 800° 900 
“TEMPERATURE 
Fig. 1 


+2000 


+1500 


+1000 


+500 


0 

a 
f) 
i=} 
— 
ee 500 

1000 

-1200 

400° 500 600° 700° 800° 900° 
TEMPERATURE 


Fig. 2. 


392 


were represented quite well by 7/og p plotted against temperature 
as a straight line as seen in the table II. 


The Melting Point of Arsenic. 

The direct measurement of the melting point of arsenic was im- 
possible in the course of this experiment, because the thermo-element 
was placed outside of the indicator. 

As shown in figure I, the observed pressures ') of the gray modifica- 
tion very near this melting point (represented by a dotted curve) 
were always a little lower than the extrapolated pressure curve and 
at the temperatures a few degrees higher than the melting point the 
indicator showed the right pressure of the liquid phase. For determining 
the melting point | have therefore extrapolated the pressure curve of 
the solid phase as that of the liquid phase and it was found between 
817° C.— 818° C. which agreed well with the value given by GouBgau’) 
and Rassow?). The corresponding pressure is 35.8 atm. Of course, 
we could find also the value of the melting point by the intersection 
of the two 7T'log p—t lines of solid and liquid phases, but in this 
case we find the following values. 

i (Q)/4.571 p 
822° C. 1710 36.5 


These values of the triple-point are certainly too high due to the 
deviation of the expression used, as was already mentioned. 

As to the pressure of the triple-point, we can measure it directly 
with a certain degree of accuracy. Arsenic shows a very large 
effect of supercooling, sometimes more than 30 degrees in the authors 
experiments. In the case of a sudden crystallisation of such a super- 
cooled liquid, its temperature rose very quickly to the melting point; 
consequently the pressure rose also suddenly several atmospheres, so 
that it was almost impossible to follow this sudden change of the pres- 
sure, applying the pressure outside the spring of the indicator so that, 
the spring broke. But if the temperature of melted arsenic was kept 
a few degrees below that of the melting point, and if the change of 
the pressure was constantly watched for a long while, sometimes 
longer than two hours, then it was possible to follow the sudden 
change of the pressure by crystallisation. In this case the pressure 
remained constant during the crystallisation This adjustment of 
the pressure, however, requires much skill, otherwise the spring 
will break. In this way we could read the pressure at the melting 


!) These values were not given in the table. 
2) loc. cit. 


393 


point, which coincided with the value found by the extrapolation 
of the vapour pressure curve of the solid phase to that of the 
liquid phase (35,8 atm.). 


The Heats of Vaporization and Sublimation of Arsenic. 

Heat of vaporization is, of course, a temperature function, but 
its temperature coefficient dQ/dt is generally negative, so that 
T log p—t curve should be concave to the straight line given by 
the expression 

Q 
4.571 
which was deduced from the assumption that Q isa constant. On the 
contrary, the present experimental results show that the 7’ log p—t 
curve is somewhat convex to the said expression of pressure, so 
that we can see that the deviation of the assumption, that Q is a 
constant, is smaller than the total effect of deviations from other 
assumptions, so that we may say that the temperature coefficient of 
the heat of vaporization is comparatively small. It is, therefore, 
possible to calculate the heat of vaporization from the expression 


T log p= — Sen GUl 


T logp=- + CT, 


4.571 
which was found to hold good for comparatively low temperatures. 
For the molecular heat of sublimation we have 
Q 
4.571 


== Sol 


hence, 
Qsq = 33.6 Kg. cal. 
For the molecular heat of vaporization for the liquid phase, we have 


Q 


= 2450 
4.571 : 


hence, 
Qz6 == 1) 7) ke. cal. 

From the difference of the above two heats of vaporization, we 
have the molecular heat of fusion 

Qs, = 22.4 keg. cal. 

According to TrovTon’s law, Lx Cuateniur showed, that the quotient 
Q/T, where Q is the heat of sublimation at sublimation temperature 
under one atmosphere and 7’ is the sublimation temperature, would 
be 30 for all substances. In the case of arsenic, the temperature of 


‘ 


sublimation is 616° C. or 889 in absolute unit, then 


394 


Q_ 33610" _ 
= ap 


This is a very high abnormal value, just as in the case of phosphorus. 


The Black Modification of Arsenic. 

It was tried to measure the vapour pressure of the black modi- 
fication by means of the same indicator as was used in the above 
experiments. But when the vapour pressure was high enough to 
measure by this indicator, all the sample in it was transformed 
into the gray modification’), so that it was necessary to find a 
suitable negative catalyser for this transformation, which would not 
disturb the pressure measurement. The author hopes to continue this 
study on a future oceasion. 


SoU Ml MARS Ye 


The vapour pressure of the gray modification of arsenic and its 
liquid state were measured. From these data, the molecular heat 
of sublimation, of vaporization and of fusion were calculated. 


In conclusion, the author expresses his cordial thanks to Professor 
A. Smits for his kind suggestion and for the excellent advice he 
has given during the work. 


Amsterdam, July 15, 1922. 


1) LASCHTSCHENKO, (J. chem. Soc., 121. 972 (1922)) gave some remarks 
on polymorphism of arsenic from the measurement of heat evolved on cooling. 


Bio-chemistry. — “On the Influence of the Composition of the 
Food on the Calcium output’. By Prof. B. Ssouiema. (Com- 
municated by Prof. H. ZwaarDEMAKER). 


(Communicated at the meeting of November 25, 1922). 


In my experiments on the influence of cod-liver oil on calcium-, 
and phosphorus metabolism [| found that the economizing effect of 
cod-liver oil on calcium and on phosphorus, was attended with a 
decreased production of faeces’). The question naturally arose whether, 
conversely, an augmented production of faeces should result from 
an increase in the faecal output of calcium and of phosphorus. 

The answer to this question is of great importance with regard 
to our understanding the metabolic phenomena and the physiology 
of the formation of faeces. The question may be looked at also from 
a practical point, especially because in experiments with milk-cattle 
results were repeatedly obtained of late years, which render it 
highly probable that among the dietetic factors the mineral compo- 
nents are often in the minimum. 

In the experiments described below we observed especially the 
influence of the increase of the quantity of indigestible foodstuffs 
(ballast) on the calecium- and phosphorus-metabolism. Two ballast- 
experiments have been performed this summer, both with rabbit II, 
which since November 1921, was always used for metabolic exper- 
iments, and which for chief diet was given a ration of dextrin, 
lactose, oatstraw boiled with acid and alkali, a calcium-free salt- 
mixture, a pure protein, viz. casein (afterward partly substituted by 
gluten of wheat) and a few grammes of butter. 

Besides this food-mixture, wheat (whole kernels) was given in the 
ratio 3 mixture to 1 wheat. In addition almost always 15 grms of 
cabbage was administered per day. For some weeks the boiled oat- 
straw was replaced by sawdust boiled with acid and alkali and the 
cabbage by mangels or carrots. 

The calcium-determinations’) were made, after destructio of the urine 
or the faeces, titrimetrically after Mc CruppEn, as well as nephelo- 


1) Jubilee-Volume ZwaarpEmAker. Arch. néerl. de Physiol. t. VII, 1922. 
4) The analyses were performed by Miss J. E. van per Zanpe, conseryatrix, and 
by Messrs H. Hoocuoupt, analyst and H. Giere.ine (volontaire). 


396 


metrically after Lyman. The phosphorus-content was determined (also 
after destruction) nephelometrically and also colorimetrically, after 
Bret and Dorsy’s method altered by Briggs. 

Both ballast-experiments consisted of: an initial, and a final period, 
each of a fortnight, in which the food-mixture contained 3°/, ballast; 
intermediate periods of a week, in which the ballast was raised to 
15°/,, respectively lowered to 3°/, and the experimental periods 
proper, each lasting a fortnight. In the first ballast-experiment there 
were three experimental periods proper, the middle one with an 
increased protein-content (10°/, gluten of wheat) and cystin. During 
this experiment 40 mgrms of Ca. (as Ca acetate) was given separately 
per day, but only 15 mgrs in the final period. In the second 
ballast-test caleium was administered separately to such an amount 
(at the most 12.7 mgrms per day) that the caleium-content of the 
food was the same all through the experiment. 

As the diet (without cabbage) was composed of 3 parts of the 
food-mixture and 1 part wheat, it contained less than 15°/, oat- 
straw, viz. 14°” °/.. F 

With a heightened percentage of ballast or protein, the procentic 
amount of dextrin plus lactose in the food-mixture was lowered in 
both experiments. 

The food was always made into a pap with boiling distilled water. 
The green-fodder, and in other cases the calcium-acetate was admi- 
nistered separately. The animal was weighed every three days. 
The weight varied from 3530 to 3570 grammes. The average amounts 
per day of calcium given off in the faeces and present in the food 
in the various periods of the two ballast-experiments are expressed 
in mgr. Ca in the following table: 


Experimental- 
period 
15/9 ballast 


Initial-period 
3/9 ballast 


Final-period 
3%9 ballast 


Ist exp. 30.4 88.4 en 69.3 12.5 
Output 

2nd exp. 44.1 66.76 | 21.1 

Ist exp. 59.— 76.— 46.3 
Intake 

2nd exp. 33.6 35.— 36.4 


It appears distinctly from both experiments that the calcium- 
output in the faeces is increased. The ratio of the output in the 
initial period to that in the experimental period in the first experi- 


397 


ment is about 100: 250; in the second experiment the ratio is about 
100 : 150. 

That in the one experiment the rise of the calcium-output differed 
from that in the other, is no doubt due to the very different amounts 
of calcium administered along with the ingested food. 

The extra-ballast in the experimental period as compared with 
the initial-period (12°/, of the fodder-mixture) amounted in the first 
experiment to about 19 mgrms per day; in the second (when no 
sawdust plus straw, but only straw was given as ballast) to only 
9.4 merms. The increase of the faecal caleium-ouiput is therefore, 
much larger than the amount of calcium present in the extra-ballast. 
That the calcium in the faeces was only for a small part derived 
directly from the food is also clear from the fact that especially 
in the second experiment the faeces contained almost twice the 
amount of calcium present in the ingested food. 

The increase of the amounts of faeces (air-dried) that were pro- 
duced in the ballast periods, was very large. 

The subjoined table gives the production in grammes. 


Initial-periods | me seeoaetT | Final-periods 
Ist exp. 5.62 11.9 and 10.5 | 3.35 
2nd exp. 3.62 | Ul? | 3.85 


The 12°/, extra-ballast in the experimental periods averaged per 
day in the first experiment about 6,6 grms, in the second 4.7 grms. 
These values do not differ much from those showing the increments 
of the faeces production. 

In the first experiment the calcium-contents of the faeces (air- 
dried) were considerably higher during the ballast-periods than in 
the initial-period; they were lowest in the final-period. (This is most 
likely due to the smaller quantity of calcinm-salts that were admini- 
stered). In the second experiment the calcium-content of the faeces 
diminished after the initial-period, which is not surprising if we 
consider the very great losses and the consequent highly negative 
balance. In the second experiment the difference between the output 
and the calcium in the food was about double the difference of the first. 

The negative balance is no doubt also answerable for the fact 
that in the final-period of the second experiment the metabolism of 
calcium was much more economical than in the initial-period. 


398 


Whereas in either period the amount of calcium administered was 
nearly equal, the output in the initial-period was about three times 
that of the final-period. When comparing the values of the fore- 
period and of the experimental period of the second experiment, 
we see that whereas the quantity of faeces was about the double, 
the Ca-loss in the faeces was about 14 times greater than in the 
initial-period. 

The caleium-output via the kidney was in the first experiment 
during the ballastperiods higher than in the initial- and final- 
period; in the second experiment there was a gradual decrease of 
calcium in the urine. This is also most likely attributable to the 
higbly negative balance. 

The figures warrant the assumption of a rise of the calcium- 
output in the urine resulting from a great amount of ballast, if the 
diet is not too poor in calcium. The quantity of calcium in the 
faeces was as a rule at least double the quantity of that in the urine. 

Regarding the influence of ballast on the phosphorus output we 
only wish to observe that it was not quite parallel to the influence 
on the caleium-output. In the ballast-periods the phosphorus-content 
of the faeces decreased considerably in both experiments. 

In a subsequent paper I intend to discuss the nitrogen-, and the 
iron-outputs in these experiments, and to give the results of the 
experiments in which we examined the influence of the alkali metals 
in the food on the calcium- and the phosphorus metabolism. 

From the experiments here described it appears: 

1. that an increase of the amount of indigestible matter in the 
food causes a greater loss of calcium via the intestinal canal. 

2. that not all the calcium present in the faeces is necessarily 
derived directly from the food: a large portion of it may be given 
off by the organism, from which we may conelude that calcium 
plays a rdle in the production of faeces. 

3. that in view of this it is only under certain conditions that 
an examination of the faeces can show whether in the food or in 
a part of it (e.g. calcium-salts) calcium oecurs in an available form. 

4. that in animals, yielding much milk, feeding with much ballast 
enhances the danger of a negative calcium balance. 


(From the Chemical Laboratory of the Utrecht 
Veterinary University). 


Physics. — “On Heats of Mixing of Normal and Associating 
Liquids.” By Dr. J. J. van Laar. (Communicated by Prof. 
H. A. Lorentz). 


(Communicated at the meeting of November 25, |922). 


5. Some Remarks. before proceeding to the case of anomalous 
components we will make a few remarks. 

a). So far we have always written n, and x, for the molecule 
values. But often m,=1—w and n,=—z2 is put, so that n, +n,—1. 
The differential quotients of w with respect to n, and n, can then 
also be calculated by the differential quotient with respect to « by 
means of the equations 

dw dw dw sare dw 
SS ee ae ; 0S Se oe Wy | ==0 
Ox * e0n: ( ) Ox 
This immediatdly follows from w=n,w, + n,w, and 
dw Owdn, dwdn, dw Es dw 
Ox On, de On, dx = On 


=— wv, + w,, 


The same thing, of course, holds not only for w, but for every 
homogeneous function of the 1st degree with respect to the mole- 
cular values n, and n, (e.g. v). 

For a homogeneous function of the OM degree with respect to 
n, and n, (e.g. w,,v,, ete.; the degree of dissociation of the double 
molecules 8 (see further), ete.) we have: 


1 ee 
dn, Oe ; ere =) Seat 
which follows from: 
08 dB 0p dp op 
= —=0 — —=—~ 4+ —( 7e). 
rr +n, eg and ae ae ae a0 (see above) 


6). We have seen that when v,*/a,—v,°Va, =0 (i.e. when the 
critical pressures of the two components are the same) Av becomes 
=O according to (3) (hence also Av, and Av,). But according to 
(1) then also 2 =O (and this holds also for w, and w,). 

Now 

y= v, + Av=n, v,° + n,v,' + Av, 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


400 


hence when Av = 0, simply : 
, P dv dv 
OC se OF 5 Saree ; ear ater 
so that then v becomes a linear function of x, viz. v=v,° +2(v,'—2,"). 
In the supposed case also the following equation may be written 
(see § 2): 
a, 


0 b 


a, 
SS SS SS Se ee 
v 5 


0 1 Y 


hence also 
hy i a RIES Rd Bs 
i.e. the critical temperature of the ‘ideal’ mixture is also a linear 
function of 2, viz. 7;= Ty + 2(T,,—T,). 
For ¢/,2 holds: 


a a (n, Va, +2, Va,)? a, a, 


— —— ’ 


9 cag Ca ee 0 0\2 2 2 
v v6 (n, v,° + n,2,°) v,° v,° 


when Va,/v,° is =Va,/v,° in consequence of the equality of the 
critical pressures. In ideal mixtures the critical pressure remains, 
therefore, constant = pz, = Pr, Whatever is the value of a. 


6. Associated components. 

For the calculation of «w we can adopt the whole derivation of 
§ 2 unchanged; it should only be borne in mind that, the degree 
of dissociation of the double molecules of the components being 8, 
and @, in the mixture, that of the pure components will be different, 
viz. B,° and 8,°. Thence 

(n, e, + 1, e's) 7 (n, ey ale Ms e's)o 

will not be =0 now. For we can write e.g. 

! 1—s ! ' ! ' ! 
Gy == : (,)a + By (6: Je = (,')3¢a + Bi (Ee (4, ga} = (e,')sga + Bids 


2 


when (e',)g is the energy constant of a double molecule and (é',), of 
a single molecule. A similar expression applies to e',. Here e’, and 
e', always refer, therefore, to single molecular quantities. The quan- 
tities g, and g, are the “pure” heats of dissociation, i.e. without 
the paris referring to the volume contraction (see further below). 
For the above expression the following equation may, therefore, be 
written : 
ny (6,—8,") a +7, (8,—8,") Vy =—=0k 

Further it should be borne in mind that a remains unchanged 
on dissociation, for on simple joining of two single molecules to 
one double molecule, a will likewise become twice as great; 


401 


hence \)’a will have the same value for '/, double molecule as for 
1 single molecule. 

The same thing is assumed with regard to the heat capacities 
k, and k,. There too — especially for larger molecules — no con- 
traction of the value is supposed. 

Thus instead of (1) the following form is found: 

, 0 Pies One 2 
w=gqt 5 Sage sae as Mees) + (» ale =) TX (OR) 


Dyn Os UV, 


The values of w, and w, are found in an entirely analogous way 
as in § 2, viz. from (cf. equation (1*)): 


(v, Va,—v, Va,)’ a a 

2 1 1 2 1 1 2 

w=gqtnn, + (p+ Saat n,Av,+| p+ SAL n,Av,, 
: Chat | 


VV, Uv, 


in whieh further: 


a, Ha a, a, ( a, a, ) et ( a, a, ) 
I= = - = =i SP ee = 
v0," ; (v,")a, (v,)a, (v,°)3,9 (v,)4,° (v,)a,° (v,)4, 


a, 7 
ee (B, —P, ) A, ’ 


= ee 
Gis TY are De, 


ay 


as 


1—8, 
= 3 (v,)a + 8, (te = (%,)gd + B, ((v,)o—(2,) 3a ) = (v,)ya + By 4,, 


so that (v,)2,—(v,),°—= (8,—8,°) A,. In this A, represents the change 
of volume (contraction), when i the mixture */, double molecule 
becomes 1 single molecule. 

This quantity A, can possess a considerable value. The pheno- 
menon of the mazimum-density of water e.g. finds its explanation 
in the great value of 4,, so that below 4°C. the thermal expansion 
is even exceeded by the diminution of volume in consequence of 
the progressing dissociation of the double molecules. Above 4° C. 
the thermal expansion will predominate *). 


k . a : ‘ 
The same thing holds for —~ Av,, so that, taking into account 
U,V, 


that also 


Av, =(v,)a,—(1') a =(v,—2,") a0 ar ((>), —(v;) 3,9 )=(Ar,) a +(8, Oy 


Av,=(?,) 4, —(v,°) 2° —=(v,—2,°) 2,0 ij (es). —(s) a0 J=(Ar,) a, Ar (3, B,") a. 


1) This explanation, given by me for the first time in the van ’t Horr-volume 
of the Zeitschr. f. ph. Ch. (Bd. 31, 1899, p. 1 et seq.) ) more than 20 years ago 
(see particularly p. 12—16), is not yet found mentioned in any handbook. Except 
for a few favourable exceptions this is also the case with many other theories, 
rules and explanations given by me. 

26* 


402 


we may finally write: 


a 
os x( TPs 1 — JaXe 
w=n,(8,—{ | 0 3F (etgoemne) |+ 
+n,(8,—8;°) E F (»+ acai) A, | + NN, (s Vitis Eg AST, 
(v,),s.° (v,) 2, Vv, v, 


n, (Av,)s0 ——_——— |n, (Av,)g,0 
+P ee a (andart (+e am (Cule 


In this the quantities 


a, a 
— 5 ey oe A ; a — Ys = 4, 
a 2 z (e+ (v, )a,o(v, y : ae (+ Bs a 


are the total (absorbed) heats of dissociation of the components in 
the mixture, on transition of '/, double molecule to 1 single molecule. 
When we further write: 


n, (8,—8,") Q, + n, (8,—8,°) Q, = 


we get finally: 
(X,Va,—v.V4,) + (p+ 


Vv, vy 


w=Qin,n, és Ee )m (Av,)3,0 + 


ae) 


+(» a ae ale (Avs)ae 


Taking the same remark into consideration in the differentiation 
as in § 2, we find from this for w, and w,: 


CC — | a0 +m,0, ae +n (Ops ake nie CV Gee) ae 


0 A 
=F (: aie ies (v,: i a — v,)8,0 


d UV 4,—v - 
| @— B,°)Q, QF cle ee 


vv, 


/ (2ass) 


mir (» - —) (Av ,)s,9 


(x UAV, Oa 
In the equation (1ass.) we now have (see above): 
Av = v—v, = 7, Av, + n, Av, =7n,(Arv,)a0 + n,(Av,)e.0 + 
+n, (8—8,°) 4, =F Ny GIy) A, 
in which the last two terms with A, and A, will be greatly predo- 


minant. Even if the critical pressures of the two components 
were about the same, so that (Av,)ao and (Av,),. will become = 0, 


» (8) 


403 


Av will remain comparatively great, because 4, and A, will retain 
their values. 

Hence in associating components the term with Av will still more 
greatly predominate in (1qss,.) than in mixtures of normal substances, 
because also g, and g, will never be great. Just as with the capacities 
of heat, these differences in the energy constants of the half double 
molecules and of the single molecules will probably be even quite 
negligible. Even more than for non-associated components now 

w a a a 


(32 =— 


aa Ja rule LO 


may be put, which values will again not differ much in different 
pairs of substances, when the critical pressures of these substances 
do not differ too much. 


7. Approximative value of ?,— ,° with small values of 
n, (Or wv). 

From the perfectly accurate equation of dissociation’) of the 1st 
component in the mixture, viz.: 


phat 2 ! Eeringloe 
(l—z) 8, Sy ee ae 
feds fat oa Pig AEE) 24% , 


in which &’, is still a function of the temperature, or also 


By; 1 a) B,* 1 
— — K. 2 -s — — ‘€ 1 ( 
aes a) z 1+8, PP esa rccpa uae 
( =i ) =i 121 -(-p: 
e 1+3 
when = ar is put, follows immediately : 


| 1 a 
ae KI +) ye ag kK, | : 4 K, 
= at = 2 (dag el 
; ae + */,4,0+ 9) Lt latss a Lee 4 


AE 
Here is evidently = = B,° (for p=0 when «=0); hence 
4 1 


8, = if a Lae? 


1) See among other things Arch. Teyler XI, 3¢ Partie, 1908, p. 44 et seq. 


404 % 
which for smaller values of w (gy) passes into 


B, = B,° (1 a IE (1 — B,°) 9); 
so that we get: 


3 . 2 d 1+ 4 
BB =", 8° —8,"") p=", 8, 8), 


Now for small values of « we may put 8,1 and ~,=8,°, so 
that finally becomes in approximation : 


(w small) 28° = —— BY (b= B.)e Sean) 
— 1 


and «8,°—s,°) may be written for 7,(@,—8,°) = (1—2) (p,— 8,°). 


8. Reduction of the formula for w in normal components. 

When we want to test the formulae derived above by some expe- 
rimental data, we can only do so with mixtures of normal compo- 
nents. With regard to anomalous components (water, alcohol, acids, 
etc.) we lack the knowledge of the quantities g and A. On the 
contrary we calculated them approximately at the time (loc. cit.) 
from the experimental results, e.g. from the volume-contraction of 
water-alcohol mixtures. We must, therefore, confine ourselves, to 
formulae (1) and (3), and when we apply these also to abnormal 
components, we shall be able to find something regarding the probable 
values of g and A from the deviations between the calculated values 
and those found experimentally. 

For Av we found (cf. besides (3), also (3°) and (3)): 


7/,m v,°Va,(1—t) 1 v,°Va, ) 
Av=n 2, ———— (Va, -Vv Ug )Va,a,— 5 (m4, +2,4,) ey 
1—*/,m aa, 2 Bes 
when 
Bap VG Mle Vay eae 
v,° Va, be V ak, Ply 


is written. Therefore, according to (1), with omission of p, w becomes: 


i ) 2/ 0 
OU F a /,m_v,° Va, (L—t) 
wn, n, = — ; 


Thy Geel vv,1—*/,m aa 
yo l 7G 1 a,\v,° 
w=n,N, a ae | — (1—t) capa {12} o(ntmet) (tay | 
Ve 0, 6 a, v ( a, 2 a,/] v, ) 


405 ° 


when in approximation m= 7: T,='/, is put. When 7R7;, is 
written for “/,.0 and 7&7; for 4/,, and further 
a, %, on, Th, 


a, Pear, a be, Tk, 
in which 6;,: 6%, can be calculated from (7%, : pz.) : (7%, : pr), we 
get finally : 


w=Tn,n, RT; ous | ay ae | 
Vo 
) , (10) 
. 1 Wi ; ; lv,° i | 
T& Ty, ‘ Tt) 4 ( LP aig at —t) (n, +2, “| | 


When equimolecular quantities of the components are used, 
no 2 — "7 /, and also 7, = 27 = '/,, and we get: 


| oy + 


Wig S=> 


RT; ee 

4 i HE (v,° + 2,°) 
1, (Tin + Th) : 

ans T, (l—r) Ja VPN a a TEED.) (1—1) (1+ ¢) ih 
as v, = 7,v,° + n,v,°, and approximately 7; —='/, (7%, + 7%,). The 
latter is strictly accurate only when the critical pressures of the 
two components are equal (see § 5 under 6). When by way of 
abbreviation 


O50 


at rege Diss Ya (Pe, + Tig) __ 
“fp (Cheech) F i 


The, 
is put, then finally with A= 2, so that w is expressed in gr. kal.: 


7 
tig = Mi Tia| 2)? + 1/441 (1-9) —/,2,1—2)(1-+-9)} |. (109) 


This formula is, of course, asymmetrical on account of 7%, only 
im appearance, in as much as we have placed v,°Wa, in v,°Va,— 
—v,’Va, outside the parentheses. If we had done this with v,°V a, 
T;, would have appeared as fore-factor, but then (pz: px)—1 
would also have been substituted for 1—\ (pz,:px,). We now hence- 
forth take t always < 1, so that that component is chosen as the 
first, of which the critical pressure is lowest. 

In consequence of the fore-factor RT), ='/, %/,.0, w is duly of 
the dimensious of an energy. Further only ratios of quantities occur 
in (107). If, therefore, the components belong to the same family 
of substances, e.g. to the extensive family of “ordinary” substances 
(critical temp. between 400° and 600° abs, y=0,9, f=7, 
h—vp:0;— 2,1, etc.), the error committed by putting »,°! v= 
= b;,: 6%, and a,:a, = ay: a%, in ct and ¢g, is certainly negligible. 


406 


For the ratios in question are about the same for all these sub- 
stances — provided only that they be in corresponding states (e.g. 
m= '*/,) — which will approximately be the case when the critical 
temperatures are not too divergent. Only in the fore-factor %/,,.0 
care has of course been taken by means of the factor 7 that the 
corrections in question are duly observed’). 

As according to (4) 


Fey NID gy Se A 


UU, 


a Av Av 
= = =AP-IR GG, aS 
Bau v 
(see above), it immediately follows from (10°) that 

Avy ] . ( 1) ) 

Ae yes me) Ne AUP eet rslane (L+ 9), . (11) 
from which Avy can be calculated (v = 1). 

When the critical pressures of the two components are equal, 
then t is =1 and w and Av both become = 0. As we already 
pointed out in our first paper, then (i.e. with very small difference 
of px, and pz) 1—t is greater than (1—x)’, so that the part with 
4v will predominate in w. But if the critical pressures differ some- 
what more, the first part will continue to predominate. As will 
appear from the calculation in the following paragraph, the part 
with Av is at most '/, of the first part, but often it is much less. 
Hence the principal term of # remains 4P, and this may be repre- 
sented by the single formula (a = */,): 

wi = A Ive = he 7 Tk, (1—)?. 

If one wants, therefore, to form an approximate idea of the value 
of the heat of mixing w, it will mostly be sufficient to calculate 
the said value of AP. 

The value of Av will sometimes be positive, sometimes negative. 
Not always are the conditions for contraction (Av negative) fulfilled 
— see § 3: “As regards the sign of Av” ete. According to the 
tables on p. 160—161, 169 and 176 of Kremann’s cited book there 
are about an equal number of mixtures of normal liquids with 
a positive as with a negative Av. Everything. of course, depends on 
whether 


Q—V¢)—*/,4,(1—1) +9) > of <9, 


1) As RT, = 8/,,4%/,. in which A is about 27/5 for ordinary substances, 
7 by 28 y 
“4/, = RT;. Now a at T='/, 7, is about 1,44, andv = 0,73 dj, so that 


we have 4/,=2%/, =7RTx. 


407 


i.e. whether (in approximation) gy is < or >1—*/, 4, (1—17). 
And, of course, nothing can be said beforehand with regard to this. 


9. Some numerical results. 

That in case of mixing of normal substances the heat of mixing 
is actually =O or very slight (+ or —), when the critical pressures 
are about equal, appears among others from the following examples 
(compare also Table V on p. 64—65 in Kremann’s book). 


CsH;Cl — C,H;Br (P, = 446 and 44,6) |\w=0to3,3(YounG1903 and Kr.) 
Dimethylaniline— m. Xylene (, » 35,8 » 35,8); + 2,8 
Amylformiate — Propylacetate (> » 34,1 » 34,8)) — 20 
p-Xylene — m-Xylene (» » 35,0 > 35,8)} — 2,0 see 3; 
p-Xylene — o- Xylene (> » 35,0 » 36,9)/ + 23 | ; 
m-Xylene — o-Xylene (> » 35,8 >» 36,9); + 20 | 


Of the many mixtures studied, of which the critical pressures 
are more or less different, we have calculated’) the following ones 
according to (10°) for a comparison with the results of the obser- 
vation. ‘ 


1. Toluene-Benzene. Here we have: 


P,, ly Pifp =e Ob; 1s 
41.6 594 14.3 8490 
47.9 562 1 iliow 6580 


2) 
= 
= 
>» 


0.932 | 0.774 | 0.880 | 1.10 1.028 


For the calculation of 2,=v,°:'/, (v,°+v,°) we may either take — 
the densities at the temperature of the experiment, or — as v,° and 
v,° will be proportional to 6;, and 6;, — introduce the above values 
of Ob; (@ is a certain numerical value). We have done the latter. 
We now find: 
w="/,< 1,1 562 (0,00462+7/, 1,03. 0,068{0,120—"/, 1,1 .0,068 . 1,744.5) 
= 2162 (0,00462 + 0,0117 | 0,120 - 0,033!) 

— 2162 (0,00462 + 0,00102) — 2162 0,00564 — 12,2 er.cal. 

Atexejew found 14,0 (from Youne follows 15,8, and Kr. found 
18,9). 


1) Both in Table 5 for w (on p. 164) and in Table 23 for Av (p, 175) the 
“calculated” values in KreMANN’s book are all inaccurate, because instead of 
the accurate formula derived by me for Av, an approximate one was used Besides 
*7/; RT; was put in w instead of @/,=4/y = 7RT,, which in itself already 
causes the values calculated for w to be twice too small. Etc. 


408 


It is seen that here the value of the term Av is about 22°/, of 
the principal term. 

The discrepancies between calculated and found values — also 
in the following examples — must be chiefly ascribed, besides to 
experimental difficulties and small approximations in the derivation 
of the formula, to the often inaccurately known values of the eritical 
pressures. Even a slight error in them gives already rise to a com- 
paratively great change in the value of (1—7r)*. 

The following value is immediately found for 4/, according 
to (11): 

av, = */,, < 1,1 X 0,068 % 0,087 = 0,00027. 

The value 0,05: 100 =0,00050 was found (see Table 21 on 

p. 160—161 and p. 175 in Kr.)’). 


2. Metaxylene-Benzene. There we have what follows. 


P, Ne Dkr Ob. DASH. T p Vy A\s a; 


35.8 622 17.4 10820 
471.9 562 Wis 6580 


0.864 | 0.608 | 0.780} 1.20 1.053 


This gives: 
w= 7/,<1,2562(0,0185 +1/, 1,05. 0,136 {0,220 -1/,1,2, 0,136. 1,608}) 

= 2351 (0,0185 + 0,0239 } 0,220 —0,065 3) 

= 2351 (0,0185 + 0,0037) = 2351 >< 0,0222 = 52,2 er. cal. 

Kremann found 57 gr. cal. The agreement is again very satis- 
factory (taking the above remarks into consideration). The term 
with Av is 20°/, of the principal term. Further: 

ar], =1/,, < 1,2 0,136 X 0,155 = 0,00105. 

Kr. found 0,15 :100 = 0,00150. The order of magnitude is the 

same in every case. 


The mixtures with CCl, as component all present deviations. Now 
CCl, is certainly associated (see also Kr., p. 68 and 140), so that 
this accounts for the deviations. 


1) It is not very clear in KrReMANN’s records whether we should divide by 100, 
or by 1/g (7,9 + v9°) = 195,5. (Cf. p. 174). In the latter case A»/, would be 
= (),00026, in perfect agreement with the calculated value. As regards Youna’s 
value, it deviates considerably from that of Kremann. He found viz. 0,16 instead 
of 0,05 °/), henee more than 3 times the value. Also for w there are often large 
differences. 


409 


Thus according to calculation the mixture CCl,—C,H, (pz = 45,0 
and 47,9) would have to give a heat of mixing = + 2,0 gr. cal., 
whereas + 21,4 was found by Youne. The valne of 4”/,, viz. —0,00130, 
found by Youne, points to a pretty great volume contraction which, 
however, does not account for the too great positive value for w. 
Also the vapour-tension line deviates here. 

The mixture C,H,—CCl, (px = 41,6 and 45,0) leads us to expect 


+ 3,9 for w, whereas w is =—8,5 according to Younc. To this 
belongs 4”/, = — 0,00070 according to the same author, and accord- 


ingly w and Av are both negative. 
3. C,H,Ac—CCl,. The calculation of this mixture may be repro- 
duced here. We have: 


| | | 
Py aie Aja Wing oak «| Vg 7 a 


| 


38.0 | 523.2 | 13.77 | 7204 | | 
0.9189 | 0.9543 | 0.9769 | 1.054 | 0.9704 
45.0 | 556.2 | 12.36 | 6875 | 


giving: 
w='/, < 1,054  556,2 (0,006577 + 
+ 1/,0,9704 . 0,0811 §0,0231—*/, 1,054. 0,0811 . 1,95432) 

= 2052 (0,006577 + 0,01312 0,0231 —0,0418?) 

= 2052 (0,006577—0,000245) — 2052  0,006332 = + 18,0 er. cal. 

Youne found — 20,1. Calculation here gives a negative value for 
Av, the correction term not being even so much as 4°/, of the 
principal term. For 4”/, we calculate: 

Av/, —1/, >< 1,054 x 0,0811 X ( — 0,187) = — 0,00067. 

The value + 0,00030 was found by Younc. Again w and Av 
(found) have opposed signs, which is strange, and renders the accuracy 
of Youne’s values somewhat questionable. (Cf. also the last Footnote). 


Let us now give a few examples of recognized associated com- 
ponents. 
4. C,H,—C,H,OH. We have in this case: 


P, Ty Obi. Wife 5 ts T gf Ve | Zs ae) be 7! 
c } 
| 


| 
0.8720 | 0.6427 | 0.8017} 1.177) 1.044 
63.0 | 516.2 | 8.194] 4230 | 


47.9 561.6 | 11.72 6582 


from which follows: 


410 


w ="/, < 1,177 & 516,2 (0,01638 + 
+ 1/, 1,044 . 0,1280 {0,1983 — 1/, 1,177. 0,1280 . 1,6427%) 
= 2126 (0,01638 4 0,02227 } 0,1983—0,0619 }) 

=2126 (0.01638 4 0,00304) = 2126 < 0,01942 = 41,8 gr. cal. 

But + 120 is found (Young). {WinkeLmMann (1872) gives —110]. 
The term with Av is here 19°/, of the principal term. We calculate 
LOT yy. 

av], =1/,, X 1,117 & 0,1280 X 0,1864 — 0,00086. 

Youne found 0, and Gurnrin + (1884). 

In the expression Av = (Av)norm+ */, (8,—B,°) A, (ef. (8) in § 6) 
4,, i.e. the volume contraction on transition of 1 double molecule 
C,H,OH to two single molecules, seems therefore to have a small 
negative value. But in w= Wnom + Q=w,r+/, (@;—," Q,= 
= 18g Teena ase A,) (ef. e.g. 1 ean § 6) Q, should 

2) 9 \U2) By 
also be negative then (leaving qg, out of account). In reality */,(8,—@,°)Q, 
seems, however, to be about 80 gr. cal., which would point to a 
comparatively large positive value of Q, (hence also to a positive 
value of 4,), but seeing the deviating value of WINKELMANN, little 
can be said with certainty about this. Indeed, we know little or 
nothing about the value of @—s,. 

5. C,H,OH—CH,OH. Here we have: 


Pr, Dhy} Obi. Lert | Tt Pp VP ae a 


63.0 516.2 8.194 4230 
718.5 513.1 6.536 3354 


0.8959 | 0.7929 | 0.8904 | 1.113 | 1.003 


This gives: 

w= "/, X 1,113 X 513,1 (0,01084 + 
+ 1/, 1,003. 0,1041 {0,1095'—*/, 1,113 . 0,1041 . 1,7929 3) 

= 1999 (0,01084 + 0,01740 | 0,1095'—0,0519* }) ; 

= 1999 (0,01084 + 0,00100) = 1999 & 0,01184 = 23,7 gr. cal. 

The term with Av would, therefore, in any case be about 9°/, of 
the principal term. Further: 

dv/, =*/,, 1,113. 0,1041 . 0.0576? = 0,00028. 

Accordingly more or less these values would have to be found, when 
the alcohols were not associated. In reality, however 4’/,=0,00004 
is found, which points to a certain volume contraction in both 


411 


aleohols. Bosr') found about 0,8 for w at 17°,3. This is considerably 
less than 23,7, so that actually heat is liberated in consequence of 
the volume contraction. 


If water is one of the components, the values of Av and w are 
generally much greater. Thus e.g. Bosk’*) (w) and Youne (Ap) found: 


a) CH,OH—H,O w= — 196 | 4”/, = — 0,030 
6) C,H,OH—H,O —114 — 0,026 
c) C,H,OH—H,O + 6) — 0,030 


To form again an idea of what actually takes place I have once 
more calculated the quantities w and Av according to (107) and (11) 
— which formula is, strictly speaking, only valid for normal com- 
ponents, but can yet in approximation be also applied for the caleu- 
lation of the normal effect also in anomalous components. I have 


done so for 
6 C,H,OH—H,O. We have then: 


P, Tr Ob; Tipped T y VP 7 | a 


0.5382 | 0.4551 | 0.6746 | 1.467 | 0.8989 
217.5 647.1 2.975 1925 


l 
63.0 | 516.2 | 8.194] 4230 | 
| 
| 


From this is calculated : 

w="), X 1,467 X 647,1 (0,2153 + 
+ 1/, 0,8989 . 0,4618 {0,8254—1/, 1,467 . 0,4618 . 1,45512) 

= 3323 (0,2153 + 0,06919 | 0,3254—0,2464;) 

= 3323 (0,2153 + 0,0055) = 8323 < 0,2208 = 734 er. cal. 

For 4’/, would be found: 

Av/, = 1/,, 1,467 . 0,4618 . 0,0790 = 0,00223. 

And thus + 734 is reduced to —114, and + 0,0022 to — 0,0026. 

The great volume contraction (for the greater part owing to the 


water) certainly chiefly determines the strong liberated heat-effect. 
We shall not enter further into this, and only briefly return to 


1) At 21° 0,007 x 1/,(82 +46) =0,3, which reduced to 17°,3 gives 0,8 (see 
the tables of L. u. B.). 

3) 50 mol. °/; =64 weight °/) gives at a) —7,77 <X1/, (18 + 32) = —194 (i9°,7) 
or —196 at 17°38. Further at 72 weight. °%, of 6) w= —3,55X !/, (18-+-46) = 
= —114 (17°,3). WINKELMANN found the same thing in 1907. And at 77 weight 
% of c) is w= +-0,50 & 1/. (18 + 60) = + 19,5 (21°) or +6 at 179,3. 


412 


the question, why the values of ¢/,2 will not differ much in many 
cases, as Katz thinks he has observed. 


10. Some remarks on the values of “/.. 

In the first place it may be stated that in w=AP-a/,2s Av, AP 
is, of course, only negligible when in consequence of great volume 
contraction in associating components (chiefly water) the term with 
«/,o4v greatly preponderates. Only then w/Av may, of course, be 


put = “¢/,s in approximation. 
But in the second place ¢/,: = 4¢/,2 is not yet always constant 


within narrow limits. A look at a table') of critical pressures is 
enough to convince one of this. In water p,= 217,5 atm.; in many 
elements (metals e.g.) still much higher. In many “ordinary” sub- 
stances, however, especially organic ones), the critical pressures will 
be about between 30 and 60 atm., as extreme values. And in many 
only between 40 and 50 atm. 

All this is the consequence of the fundamental atomistic values 
of Va and 6, from which the values of Va and 6 for the molecule 
can be calculated additatively in all compounds according to fixed 
rules (see my papers on this subject already cited in 1). 

As an example let us take the following principal elements, of 
which organic substances are built up. 


H (G N Pe OFS ey CI Br I 


1056 = 34(14) 100(75) 60(85) 140 70(50) 125 55 110 165 220 
10? Va = 1.6 3.1 2.9 6.4 2.8 6.3 2.8" (55477 1629 9 


103 b/)q=21(9) 32(24) 21 22 25(18) 20 20 20 24 24 


And as the values of °/j,, do not differ so very much, this will, 
of course, not be the case either for the compounds built up of 
these elements, since — as was already mentioned — the values of 
b and Va can be additatively calculated from the fundamental values 
recorded above. 

Before concluding I will just draw attention in this connection 
to the fundamental values of a in carbon. In four single bonds 
the C-atom is towards the outside quite shaded as regards its attract- 

1) Cf. eg. p. 7 of my first Paper on the additivity ef b and Va in the J. d. 
Ch. ph. (1916) or These Proc. Vol. XVIII N°. 8 p. 1220 et seq. 


413 


ive action, by the surrounding atoms or atom groups (Examples 
CH,, CCl,, C,H,, CH,Cl, CHCl,, etc., etc. — ef. also p. 22 J. d. Ch. 
ph.; also SnCl,, GeCl,, etc.). 

In double bonds, on the contrary, part of the C-atom are left 
free again, and is 10*\)/a—1,55, exactly half*) of the normal value 
3,1. In triple bonds the whole C-atom can exert an attractive action 
towards the outside, so that then 10°?Va= 03,1. 

Accordingly in the compound under consideration the value of 
10? Va is 1,55 greater for every C-atom with double bond, than 
corresponding single bond. The amount of energy e, which contains 
the term —/,, will, therefore, be smaller by a proportional value. 
Wrsaut (Ch. Weekblad N*. 24 of 17 June 1922, p. 259) really 
states that the value of the energy of a double bond is from 10 
to 20 cal. smaller than in a single bond. All this finds its explana- 
tion in the theory concerning a and 6 for all possible kinds of 
compounds given by me in 1916, which theory has, unfortunately, 
remained unnoticed by many up to now. 


Tavel sur Clarens (Suisse), Sept.—Oct. 1912. 
1) Thus e.g. in all aromatic compounds, in C,H, etc.; compare the table on 
p. 20 J. de Ch. ph. 


Physics. — “On Wuirraker’s Quantum mechanism in the atom’. 
By Prof. H. A. Lorentz. 


(Communicated at the meeting of October 28, 1922). 


§ 1. Some months ago Wuirrakrr') has proposed an interesting 
model by means of which the quantum properties of the atom can 
be accounted for to a certain extent, the model showing in the first 
place bow it may be that, in the collision of an electron against 
an atom, the former loses either no energy at all, or just a definite 
amount of it. In what follows I shall offer some remarks about the 
action between an atom and an electron, as it would be according 
to WHITTAKER’sS views. 

WuirTaker supposes that, when an electron approaches an atom, 
a “magnetic current” is set up in this particle, comparable with the 
electric current that is excited in a diamagnetic particle by the 
approach of a magnetic pole. In this latter case the induced current 
makes the particle repel the pole (Lenz’s law) and similarly in the 
former case the magnetic current gives rise to a force tending to 
stop the motion of the electron. 

The theory takes the simplest form when it is assumed that there 
are not only ‘‘electric charges”, but also “magnetic” ones, accumu- 
lations of positive or negative magnetism. By the introduction of 
these into the fundamental equations, the parallelism between the 
electric and the magnetic quantities can be clearly brought out. 


§ 2. Let @ be the density of the electric charge, v the velocity of 
one of its points, and similarly mw the density of magnetic charge, 
w its velocity; furtber d the electric force or the dielectric displace- 
ment in the aether, and h the magnetic force or magnetic induction. 
Then we have the fundamental equations 

div'd|=0;, 1s) 0) ae (1) 
doh", . . >” =e) 


roth =— (4+ ev) ME cs et (8) 


rod = ——(h + aw) - Me) om )) 


1) E. T. Warrraker, On the quantum mechanism in the atom, Proc. Royal 
Society Edinburgh 42 (1922), p. 129. 


415 


The foree with which the field acts on unit of electric charge is 
given by 


1 
and there is a corresponding force 
1 

Be eke MeO: - ee eee tO) 


acting on unit of magnetic charge. 

Remarks on the fundamental equations. 

1. In order to simplify the mathematical treatment all quantities 
occurring in the equations are considered as continuous functions 
of the coordinates. 

2. We shall suppose that, while points of an element of volume 
move with the velocity v varying from point to point, the electric 
charge of the element remains constant, so that the density 9 changes 
in the inverse ratio as the size of the element. We shall make a 
similar assumption concerning the magnetic charge. By these assump- 
tions the distributions, both of the electric current d+ 0Vv and of 
the magnetic current h+ mw are made to be solenoidal, as they 
must be if equations (3) and (4) shall be true. 

3. For the sake of generality we have introduced different sy mbols 
v and w for the velocities of the electric and the magnetic charges. 
These charges may be imagined as penetrating each other and 
having independent motions. 


§ 3. The fundamental equations form a consistent system and 
are in good agreement with ideas and theorems which physicists 
would be very unwilling to give up. 

The force acting on the electric and the magnetic charges con- 
tained in an element of volume, taken per unit of volume, is 
given by 


1 1 
ef -He—ed +eh+—-lew-h] — — lew. d] 


and for the z-component of this foree one finds after some trans- 
formations 
. OX, OX, OX. dG, 
SE irae ae oe a 


where 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


416 


X, = 3 (axe as d, <7 d.’) } 4 (h.” = h,’ Bows h.’), 
Xy ——= 10 fs d, + he h,, <— d. d- + hi h., etc., 


1 
G=—[d.h]. 


This shows that the ponderomotive forces can still be expressed 
by means of Maxwett’s stresses and of the electromagnetic momen- 
tum G. It should be noticed that this is possible because we have 
the positive sign in (5) and the negative sign in (6). 

The well known expressions for the electric and the magnetic 
energy and for the flow of energy likewise remain unchanged. 
Indeed, starting from the fundamental equations, one finds for the 
work, per unit of time and unit of volume, of the forces exerted 
by the field 


dE : 
(of.v) + (ug-w)= — apr tS? 
E = }4(d* +h’), Si cid oni 


§ 4. If the distribution and the motion of the charges are known, 
the field can be calculated by means of two scalar potentials ¢, x 
and two vector potentials a,b. These functions are given by the 
formulae 


1 (tel 1 (te) 
o=|— |— = ds; == == 1S, 
i =| a Ax) 1 : 
1 1 
|= = ‘| lev] d8, b= ew] ds, 
4x r 4ae r 


in which the integrations have to be extended over all space. The 
distance from the point for which one wants to determine the poten- 
tials for the time ¢ is denoted by 7 and the meaning of the square 
brackets is that the quantities @, ete. have to be taken such as they 


; r 
are at the time ¢ — —. 
c 


In terms of the potentials we have for the field 


ee 
d = — —a — grad g — roth, 
¢ 


es 
h = — —b — grad y +- rota. 
c 


§ 5. We shall now suppose, following Wuirraker, that in the 
atom there is a circular ring &, over which magnetism is uniformly 
distributed. We shall consider it as very thin, so that we may speak 


7 
d 


417 


of a ‘line’, and we shall denote by a the radius and by & the 
amount of magnetism per unit of length. Let the centre O be taken 
as origin of coordinates, the axes VU Y and O Z being in the plane 
of the circle, and let s be the distance from a fixed point, measured 
along the circle. The positive direction of s will be determined by 
the rotation O Y ~ OZ, and will therefore correspond, as we 
shall say, to the direction of OU X. We shall finally suppose the 
ring to be a rigid body that can only rotate about O X, and we 
shall in the first place calculate the couple acting on it when an 
electron with charge e moves in the neighbourhood. 

The force on an element ds is /£gds and its moment with 
respect to O X akg,ds=akh.ds. Thus the resultant couple is 


ak | h,ds, where the value of the integral may be deduced from 


(3). For this purpose we imagine some stationary surface 6 having 
the circle A for its boundary and the normal x to which is drawn 
in a direction corresponding to the positive direction of s. Then, if 
this surface does not intersect the electron, 


eae igre ie 2h (yg, 7 
fn: =| n ¢ eae | MLO e019 so) To) pare (7) 


We shall suppose the motion of the electron to be so slow and 
to change so slowly that it may be said, in any of its positions P, 
to be surrounded by the electric field that would exist if the electron 
were at rest in that position. Then the last integral in (7) has the value 
e ; : d 
7D if w is the solid angle subtended at P by the ring R, the 
1 4 
sign of w depending on the direction, towards the positive or the 
negative side, in which straight lines drawn from P pass through 
the surface. Hence, the equation of motion of the ring will be (® 
angular velocity, Q moment of inertia) 


dd ake dw 
Q— 


dt 4ac dt (®) 


If this equation is to hold for a certain lapse of time, the surface 
6 must be chosen in such a way as not to be traversed by the 
electron during that interval. 

Now, two cases must be distinguished, the electron passing or 
not passing across the circular plane within the ring, or, as we 
shall say, through the ring. In the latter case, 6 may be made to 
coincide with the circular plane and we shall bave, both before 
and after the encounter, if the electron is at a great distance, 


yjTs 
27% 


418 


w=0. In the former case this will not be true. Let us suppose 
that the electron goes through the ring once, in the positive direction, 
and let A and B& be two positions, before and after the encounter, 
both far away from the ring. Then, whatever be these positions, 
provided only that they do not coincide, we can choose the surface 
6 in such a way that it is not intersected by the path of the 
particle from A to B, and that w =O at the point A. It is easily 
seen that then the final value will be w = 42. 
Bij integration of (8) one finds 
ake 


tot pag? «ate asp i) 


if J, is the angular velocity which the ring may have had before 


the encounter. 


§ 6. We have next to consider the motion of the electron. The 
rotation of the ring constitutes a magnetic current 
t== oh) nal 1 wees CO) 


giving rise to an electric field that is easily determined if we sup- 
pose it not to differ appreciably from the field that would exist if 
z were constant. The calculation, exactly similar to that of the 
magnetic field due to an electric current (the vector potential b is 


first determined and then d= W— rotb) leads to the result 
d i Ow on i Ow d i Ow Wl 
7 Ageede’ 9% Baecdy” \)o oan Ciro ee man Ory 


from which, combined with (10) and (9), we can deduce that the 
force ed acting on the electron depends on a potential 
ake a?k? ¢ 


=— 0 ———_—w? ., ... . (12 
4c 0 Ost oa iQ ae Nad 


yw 


If we wanted exactly to determine the motion we should also 
have to take into account the force with which, owing to its velo- 
city, the electron is acted on by the magnetic field that is due to 
the ring and to stationary magnetic charges eventually existing in 
the atom, and so the problem would become very difficult. Since, 
however, the latter foree does no work, we can write down the 
equation of energy 


mo? = dan 0,7 = by) yo) LS) 


(v, the initial velocity at a point where w =O) and this is sufficient 
for some interesting conclusions. 


419 


Indeed, if the electron has not passed through the ring, we shall 
have finally o=0, yw=0, so that at the end of the encounter the 
angular velocity of the ring and the velocity of the electron will 
again have their initial values %,, v,. This will also be the case if 
the electron goes twice through the ring, first in the positive and 
then in the negative direction. 

If, however, it goes through the ring no more than once, the 
final value of w will be +a and according to (12) and (13) the 
electron will have lost an amount of energy 

ake a’ k? e? 
ching 20c?Q 

The ring will have gained just as much. This follows directly 
from (9) and also from the remark that, as may be seen by (9) 
and (13), 


imv’+4Q9* 
remains constant during the motion. 
In the case ¥%,=O the energy that is imparted to the ring by 
an ‘effective’ encounter is given by 
a* k* e? 
2c? Q 
This agrees with Wuirraker’s result. In his calculations he has 
confined himself to a motion of the electron along the axis of the 
ring, but the preceding considerations show that the theory can 
easily be generalized. However, it is also seen that, if in an effect- 
ive encounter the ring is to receive the amount of energy repre- 
sented by (14), the rotation which may have been imparted to it 
by a previons encounter, must first have disappeared in one way 
or another. 


(14) 


§ 7. If, in the case & —0, the electron is to pass through the 
ring for good and all, it must initially have at least the amount of 
energy (14). If it has less, it can by no means get beyond a point, 


where 


NEC, ,— 
ZV) “tame sh lo) 


aQ—— 
are 


Such a point is really reached, the electron returning after having 
got to it, when the motion is along the axis. In general, however, 
the problem is less simple. The locus of the points which satisfy 
the condition (15) is a surface limited by the circle & and having, 
for a somewhat high value of v,, the shape of a wide bag lying 
on the positive side of the circle, which forms its opening. An 


420 


electron that flies into this bag can never leave it across the surface 
which it will perhaps not reach at all. Indeed, it may be that, 
before the velocity is exhausted, its direction comes to be tangential 
to a surface w = const., characterized by a value of w smaller than 
the one given by (15). It seems probable that in such a case the 
electron, after having moved in the bag for a certain length of time, 
will leave it through the opening, but it is difficult to make sure 
of this. *) 


§ 8. In Wuirraker’s model the ring R is made up of the poles, 
of equal signs, of a number of magnets arranged along radii of the 
circle and having their opposite poles at or near the centre. It might 
seem at first sight that in a structure of this kind the magnets can 
be replaced by perfectly conducting solenoids carrying pre-existent 
electric currents, so that we can do without magnetic charges. 

In reality, however, no satisfactory model can be obtained in this 
way. This is seen most easily when the electron is supposed to 
move along the axis 0 XY. In the magnetic field due to this motion 
the lines of force are circles around the axis, and therefore the force 
acting on an element of current at a point P, is directed along a 
line lying in the plane P OX. For such a force the moment with 
respect to O X is zero; consequently, neither a solenoid nor a system 
of solenoids can be acted on by a couple tending to produce a 
rotation about OX. 

Thus it would seem that the hypothesis of “magnetism” existing 
independently of electric currents is quite essential in WaurrakeEr’s 
model. I need not speak at length of the reasons for which such an 
assumption is not to be readily admitted. Let it be remarked only 
that the equations (1)—(6), though forming a consistent system, do 
not allow us to establish variation theorems of the kind of Hamiron’s 
principle. In this principle we are concerned with the difference 
between the potential and the kinetic energy, so that, in the equations, 
the two energies do not occur in the same way. Now, if there are 
only electric charges, we can, as is well known, arrive at an equation 
of the Hamiltonian form, in which 34d? takes the place of the 
potential and $h’* that of the kinetic energy. If there are only magnetic 
charges, there is a similar formula, in which, however, the electric 


1) An interesting discussion of this question has been given (Phil. Mag. 44, 1922, 
p. 777) by Mr. B. B. Baker, wo has considered the case of an electron not moving 
along the axis of the ring, without, however, taking into account the forces that 
may arise from the existence of a magnetic field. 


42) 


and the magnetic energy have changed their parts. It is clear that 
it must be difficult to combine the two theorems into one. 

I must not omit to say that Wuirraker does not want to attach 
too great importance to the special form of lis model. He aptly 
remarks that, after having obtained a satisfactory system of equations, 
we may discard the model by which we have been led to it. What 
is especially interesting in Wuirrakrr’s idea seems to me to be this, 
that it shows the possibility of a sharp criterion by means of which 
it can be decided whether an encounter is effective or otherwise. 
Such a criterion there must certainly be. 


§ 9. Generalization of the model. Suppose that there is in the 
atom a definite closed circuit s, in which a magnetic current 7 may 
circulate, the energy being } Lz’. Then we have the differential 


L i = h; ds, 


or, if an electron moves near the atom, 
di e dw 
ae ae Te 
Take this instead of (8), and combine it with (11). The amount 
of energy that is transmitted in an effective encounter (initially 
i= 0) is now found to be 


e 
27D - 

In order to obtain a ‘“vibrator”*) we can link the circuit s with 

another circuit s’, in which an electric current can circulate (no 


resistance, energy 4 L'v'?); indeed, we have 


(16) 


iteelio: _ di! 1 
Ss 5 5 = — —7. 
th, dt c 
The frequency is given by 
1 
Aa Adiiae 


If now an electron passes through the circuit s in a time that is 
short in comparison with the period, the vibrator receives the 
amount of energy (16) and this amount will subsequently be radiated. 
It will be equal to hy if 


1) Cf. Wuittaxer, l.c. § 5, p. 139. 


422 


One -can also try to illustrate other phenomena by means of the 
model. In its passage from one stationary state of motion to another 
an electron may be imagined to go through the circuit s of a 
vibrator, so that the energy which it loses is first imparted to the 
vibrator and then radiated by it. Conversely, after having taken in 
some way from a beam of incident light the energy hy, the vibrator 
could give this energy to an electron that passes through it at the 
right moment. But in all this we are confronted with very 
serious difficulties. 


Psychiatry. — “Concordance of the Laws of some Psychological 
and Physiological Phenomena’. By Prof. E. D. Wrersma. 


(Communicated at the meeting of September 30, 1922). 


The phenomena of consciousness are attended with material 
changes in the brain. There is an uninterrupted continuity in the 
anatomic as well as in the psychic phenomena. The two groups of 
phenomena run parallel. A change in the one will be accompanied 
by a change in the other. Whether we consider the phenomena of 
consciousness from the psychological or the physiological standpoint, 
in both cases the result will be the same, because the changes in 
the one differ from those in the other not intrinsically but only in 
form. Memory, which we conceive to be the retention and repro- 
duction of previous impressions, has been considered physiologically 
and psychologically. First Arisrorien and afterwards Hering have 
looked upon it as a general function of the organised matter. SEMoN, 
who has written a pre-eminent monograph on the Mneme, deemed 
the ordinary terminology inadequate, as it concerned chiefly the 
phenomena of consciousness. He, therefore, introduces other terms, 
as engrams, i.e. the organic changes evoked by a stimulus; the 
retention of those impressions, which afterwards may again come 
to us as consciousnesses, is the mneme; and the stimuli by which 
the action of the primary stimulus can be re-aroused, are termed 
ekphorie stimuli. Under certain conditions permanent connections are 
formed between the several engrams, which have been termed 
“regular tracks’. By the side of this anatomical interpretation the 
psychological explanation may be put forward. We know for certain 
that every impression leaves an after-effect in consciousness. Mental 
tests on secondary function, psycho-analysis, the symptoms of hysteria, 
hypnosis have conclusively established the existence of these after- 
effects. That these after-effects may become consciousnesses again 
through association, is borne out by self-observation and by experiment. 
Thus the psychological conception may be formed directly, whereas 
for the physiological we have first to pre-suppose all sorts of organic 
changes, for we are still completely ignorant of the real existence 
of the organic engrams and the regular tracks. In strictness this 


424 


interpretation is physiological only on the outside; at bottom it is 
psychological. 


Emotions reveal themselves in two ways: Self-observation tells us 
what emotion in reality is, and from the expression of emotions we 
deduce what the feelings of the affected individual really are. We 
know that these peripheral phenomena play so important a role that 
some regard the expression of an emotion in reality as the source 
of emotion, as a conscious progress. Many psychologists still adhere 
to this ‘James-Lance-theory”. However, Leamann has shown by dint 
of many arguments that emotion is primary and expressional 
movement is secondary. One of his arguments is that the change in 
the blood-supply, in respiration ete., is posterior to the real emotion. 
The experiment upon which this argument is based, is open to 
objection, as it is often difficult to make out where exactly the change 
in the plethysmogram or the breathing begins. This induced me to 
repeat the experiment registering at the same time the psychogalvanic 
reaction. In comparing the plethysmogram with the psycho-galvano- 
gram the latter appears to be more reliable, as is borne out by the 
subjoined curves. 


Respiration 


WPAAAKS UWI a yl V 


Galvanogram 


Plethysmogram  (\¥ Se ANIMA 
ae BPA CCT ub 


ANN ANNA ANNA 


The beginning of the reaction is clearly marked, whereas in the 
plethysmogram it is often doubtful with which pulsebeat the reaction 
really begins. The subjoined table also clearly indicates that the 


Physiological reactiontimes to pain-sensations 
in "/h 00 sec. 


Galvanogram | Plethysmogram 
220 335 
230 360 
210 280 
| 
210 350 


425 


reaction-times of the psycho-galvanogram are shorter and much 
more constant. 

These physiological reactions times, of which I mention only a 
few, are considerably longer than the psychological reaction times 
to pain-stimuli which occur directly after the toueh-stimuli. 

Thus, although emotion i.e. the psychical, is to be considered as 
primary, it is nevertheless a fact that the expressional movements 
largely influence the nature and the intensity of emotion. Intense 
emotions become less vivid through strong expressional movements. 

Having a good cry and screaming lessens our grief, hysteric 
affective conditions, which accompany weeping and screaming are 
of short duration, the raptus melancholicus has soon spent itself. 
Here we have to do with an inhibitory process of two co-existing 
complexes of consciousness. The experience of the violent expressional 
movements inhibits the emotion. 

This accounts for the custom among some uncivilised peoples of 
dissipating’ grief by selfmutilation. Not only involuntary but also 
voluntary expressional movements inhibit emotion. The intensity 
of a sad mood is often lessened by assuming the attitude and the 
countenance of cheerfulness. 

So far we have seen that conscious as well as unconscious 
will-acts bear upon emotion in the same way. Conversely, we will 
now discuss the way in which emotion affects the will-acts. 

Emotions exert a great influence upon other complexes of con- 
sciousness. They largely inhibit them, because attention clings to 
them tenaciously. Regular thinking is impossible. Voluntary move- 
ments are also inhibited. We don’t get on with our work, all our 
activities slacken, and in pathological cases, such as melancholy, a 
complete relapse may ultimately set in. Again, this does not apply 
to voluntary movements only. Also the unconscious efferent impulses 
are subject to the same influence. Cannon') showed that in cats, in 
a state of emotion, the food remained in the stomach longer than 
in that of normal cats. Similar inhibitory processes occur in man. 
A melancholiac secretes less saliva and fewer tears. This can be 
established experimentally. 

Furthermore a distinct decrease of motility of the stomach and 
the intestine is demonstrable in man. When administering 0,1 1. K. 
in the empty stomach according to Santmi's’) prescription, iodine 
will be found in the urine and in tle saliva under normal condi- 
tions after 15 minutes. According to Sanri [. K. is not resorbed 


1) Gannon - Bodily Changes in Pain, Hunger, Fear and Rage. 1918. 
3) Santi: Klinische Untersuchungsmethoden I, p. 564 u. p. 568. 


426 


at all in the stomach, or only after a long interval, so that with a 
decreased motility of the stomach the I-reaction in urine and saliva 
will appear later than in normal cases. This experiment was per- 
formed with some melancboliacs and with some normal persons: 


lodine-reaction in urine | lodine reaction in saliva 
Melancholy Normal | Melancholy | Normal 
A 105 min. | K 15 min. A — min. | K 15 min. 
B 105: 55, L 15555 B 165; , L 45: |, 
Cc 90 , M 150% Cc SO; M 15" 5 
D 00 =. N 155, D —" oy N 15 ie 
E 1h O ey E SOEs, O Gens 
F ayer F 45.15; 
G 45 5 G SOM; 
H GOne. H 60 , 
I ADE. I 45) 


This table shows distinctly the retardation of the reaction in 
urine and saliva in cases of melancholy. It is very well possible 
that this retardation is not due only to the gastric function, but 
that at the same time a slower resorption has taken place in the 
intestine aud inhibition in the seeretion of the kidneys and the 
salivary glands. 

Conclusive evidence regarding the retardation of the movement 
of the stomach and the intestine can be afforded by Réntgenograms. 

In the morning 150 grs of bariumsulphate was administered with 
500 grs of porridge in the empty stomach. Normally the stomach 
will then be quite empty again after 4—6 hours. In the stomach 
of a melancholiae I found after 4 hours still a very large quantity; 
after 10 hours a rather large quantum and after 24 nours still 
distinct traces of the bariumsulphate. After a 10 hours’ fast this 
patient took food again, so that the bariumsulphate, then present, 
may have been mixed up with the food. The latter registration, 
therefore, is not quite reliable. 

The decreased motility of the intestine also manifests itself distinetly. 
Under normal conditions all the bariumsulphate is removed from 
the small intestine after 10 hours. The examination of another 


427 


melancholiac proved clearly that after this lapse of time still con- 
siderable amounts are present. 

In the same way slower motility of the large intestine can also 
be established. In one patient the food remained in the large intestine 
for 4 days, in others for more than 5 days. 

It is evident that relative to the emotions the conscious will-acts 
and the unconscious centrifugal impulses are subject to the same 
rules. 


In discussing the reflexes it appeared that mutual inhibition of 
co-existing phenomena of consciousness also applies to simultaneous 
unconscious centrifugal impulses. Bapinski’s reflex is superseded by 
the normal plantar retlex, the sucking- and the gait-reflex by other 
movements, arising later, the diminution of the patellar reflex is 
the result of centrifagal impulses that are always present, the tonus 
of the antagonists diminishes through contraction of the agonists. 
All this proves that the co-incidence of involuntary efferent impulses 
gives rise to a mutual inhibition in precisely the same way as with 
the co-incidence of conscious will-acts. Hereby a complete co-opera- 
tion of the muscles is rendered possible. 


Closely ‘related to this are the associated movements. When a 
child begins to grasp at things with the right hand, the left one 
accompanies it. A few years later these ‘co-operations” disappear. 
They are inhibited. Whence does this inhibition arise? An incessant 
flux of impressions passes from the extremities to the area of con- 
sciousness, imparting information regarding attitude and position of 
the limbs, so that the easiest attitude will be selected and every 
undesired movement will be counteracted. At first this occurs arbitra- 
vily, afterwards involuntarily and reflexly. A gymnast and a skater 
will first try to counteract the unnecessary movements, afterwards 
this happens involuntarily. That the inhibitory action is exerted by 
these simultaneous centrifugal reflex impulses may be gathered from 
the following facts : 

Associated movements are strongest in the first years of life. 
When the position reflexes begin to develop, the associated move- 
ments will gradually cease. 

They will recur or intensify in highly emotional situations. The 
pre-occupation resulting from them will not only eliminate all com- 
plexes of the central area of consciousness, but also the subliminal 
position-reflexes will be affected by them, so that the associated 
movements of a deeper level will recur. In the same way in con- 


428 


ditions of dementia, as with dementia paralytica and dementia senilis, 
in which a general diminution occurs of the degree of consciousness, 
the position-reflexes are affected prior to the associated movements. 
it is obvious, therefore, that the associated movements will recur. 

Associated movements manifest themselves most distinctly with an 
affection of the pyramidal tract, because then the conduction of the 
centrifugal impulse, which acts inhibitively, is lacking. This is easy 
to demonstrate in patients with cerebral hemiplegia, because in these 
cases the associated movement of the paretie leg can be directly 
compared with the movement of the healthy leg. In my investigation 
[ availed myself of the following associated movement. When a 
subject, in dorsal position, is instructed to raise the right leg, the 
left leg will be pressed down, of which fact the experimenter may 
readily convince himself by putting his hand under the left heel. 
A distinet pressure will then be perceived, which will increase with 
a greater effort of the right leg. The associated movement of the 
left lez may be reinforced by opposing a resistance to the movement 
of the right leg. The registration of the associated movement happens 
in the following way. The left leg is suspended in a loop a little 
way above the heel. The loop is attached to a steel-yard by means 
of a cord that passes over a pulley. When the leg is pressed down 
the foree of the effort can be read accurately from the*steel-yard. 
To the cord is fastened a stylus, which records the movement directly 
on a rotating kymograph. In patients with cerebral hemiplegia the 
associated movement on the paretic side appears to be much more 
pronounced than on the healthy side. In the subjoined curves A’, 
A" and A" represent the associated movements of the normal leg; 

i, Ae NE iar AY 


Associated movement 
of the normal leg. 


We Y ie ae NaS B’ Associated movement 


of the paretic leg. 


I. 
acai. com Here MS A” Associated movement 
“ ae ee —_—— -— of the normal leg. 
ie i aK 4 Rie) { B” Associated movement 
ll of the paretic leg. 


\ e: \J ret A’”’ Associated movement 


of the normal leg. 


CG b’”’ Associated movement 
= of the paretic leg. 


499 


B’, B" and B” those of the paretic leg. In curve I the associated 
movement is registered without any impediment to the other leg. 
In curve II the leg is weighted with 1700 grms, and in curve II] 
with 2900 grms. 

The annexed table also shows clearly that the associated movement 
of the normal side is invariably inferior to the one on the paretic 
side. 


Curve I Curve II Curve Ill 
normal paretic normal paretic normal paretic 
leg leg leg leg leg leg 
gr. gr. gr. gr. gr. gr. 
162 167 225 975 1247 1175 
490 767 427 873 1302 1201 
438 751 592 876 1064 1453 


Associated movements are on a par with the associations of the 
phenomena of consciousness. As known, the laws under which these 
associations originate have been reduced to the simultaneous 
associations. That this is also the case with the asssociated movements 
is evident. The child begins to stretch both hands when grasping 
at something, which evolves a simultaneous association. When, in 
later years the grasping right hand is accompanied by a movement 
of the left one, this is in reality an association effected in precisely 
the same way, in which e.g. the image of a person is called up 
when hearing his name. 

Associations can be facilitated or inhibited. In this also the asso- 
ciated movements bear so close a resemblance to associations, that 
the two processes must be considered analogous. 

Associations are inter alia facilitated by greater intensity of the 
associated ideas. ExssincHaus introduced meaningless syllables to be 
learned by heart in a certain order. Reproduction in a reversed 
order was not possible. Of this Minsrerserc has put forward an 
explanation: In reciting the alphabet, a and b remain for some time 
in consciousness. In hearing b there is still a faint after-effect of a. 
Therefore, in hearing a, b will be reproduced sooner than, conver- 
sely, a will be reproduced in hearing b. In the associated move- 


430 


ments the same phenomenon manifests itself. The intensest associated 
movements persist longest. They display a much greater resistance 
to the inhibiton. There are people with whom some associated 
movements persist through life e.g. the mouth-movements when they 
are using scissors. 

Associations are also promoted by the intensity of the associating 
idea. Memory-images will be reproduced the more readily according 
as the associating idea is more intense and distinet. Experience e.g. 
teaches us that visual, and auditory sensations arouse associations 
sooner and more distinetly than the vague olfactory, and gustatory 
sensations. We can observe a similar phenomenon in the associated 
movements. The curves obtained from the above experiments go to 
show that, when the movement of the one leg is interfered with 
by a weight thus inciting the subject to greater exertion, the asso- 
ciated movements of the other leg also increases. 

In curve Il the weighting of both the paretic, and the normal 
leg considerably increased the associated movements on either side. 
When, as in curve III the weight is very heavy, the demand upon 
the paretic leg is so great, that the ensuing associated movement 
of the normal leg does not differ much from that of the paretic leg. 
Curves I and II also demonstrate that, with a series of movements 
of the paretic leg the associated movements of the normal leg 
increase in maguaitude. This is due to a greater demand upon the 
paretic leg consequent on fatigue. 

The associations of the phenomena of consciousness can also be 
inhibited. Here again the associated movements exhibit analogous 
phenomena. As known, the association of the phenomena of con- 
sciousness is interfered with by co-existing complexes of conscious- 
ness and the degree of the interference depends on their homogeneity. 
The reproduction of visual ideas is counterected by other sight- 
experiences in a higher degree than e.g. by auditory experiences. 
In forming a visual image of a situation, we shut our eyes. Speaking 
a foreign language is more difficult than to read it, because the 
word in our native tongue arouses many associations which act 
inhibitively, whereas the foreign word awakens na other associations 
than those called up by the native word. It is just the same with 
the associated movements. The impulses exciting them, are ousted 
already by the co-existing efferent impulses of the position reflexes. 
It is evident, that also here there is an analogy to the inhibition 
exerted upon sight-associations by other visual impressions, and to 
the inhibition, exerted by the multitude of associations, upon our 
efforts to speak a foreign language. 


431 


The so-called mediate associations occur, when memory-images 
flash into consciousness that seem to have no connection with the 
associating idea. On closer inspection it will appear that the associ- 
ated idea has not linked itself directly to the associating idea, but 
to an unconscious memory-image. Without this intermediary the 
association would not have originated. The strange freaks of normal 
men, of hystericae and in cases of dementia praecox, may often be 
assigned to these intermediary ideas unsuspected at the moment of 
the association. Afterwards they crop up again by concentrating 
ourselves entirely upon the association, or by other means, such as 
association experiments, hypnosis, etc. Similar phenomena occur in 
physiological processes. Many renal diseases are attended with hyper- 
trophy of the heart. The real relation is still a moot point; probably 
the enlargement of the heart arises from the increase of the blood- 
pressure, which some believe to result again from the retention 
of the intermediary products of metabolism, or, according to 
others, from an excess of adrenalin-products. It is evident, then, 
that here also we have to do with two phenomena mediately con- 
nected. A similar example is afforded by hypertrophy of the uterus 
in pregnancy. This is not a direct action of the foetus upon the 
uterus, as this hypertrophy also reveals itself in extra-uterine preg- 
nancy. Now, inquiries have proved that most probably internal 
secretion of the corpus luteum comes into play here. So, here again 
we observe a connection between the two phenomena, through the 
mediation of one that has long remained unsuspected. The hyper- 
trophy of the mammary tissue in pregnancy is assignable to the 
same cause. 

We have already referred to the phenomena of ousting the centri- 
fugal impulses by conscious will-manifestations and even by other 
reflex-impulses, nearer to the threshold of consciousness. Definite 
proof of it is afforded by the superseded reflexes, as that of BaBinsk! 
and the sucking reflex, and the superseded associated movements. 
As stated above, these reflexes have not disappeared; they recur 
when the inhibitory influences do not exist any more. In this respect 
they resemble retrograde amnesia. Here also memory images are 
stamped out by intensely operating, often highly emotional, impres- 
sions. The memories closest to the threshold of consciousness, still 
exerting their after-effect upon the centre of consciousness (which 
peoves them to be still coexistent with the superseding stimulus), 
are thrown back farthest from the view-point. We may, then, put 
it in this way that Herymans’s ingenious idea is applicable to the 
superseded reflexes as well as to the superseded thoughts, viz. 

28 

Proceedings Royal Acad. Amsterdam. Vol. XXY. 


432 


that their distance-energy is enlarged and their level-energy has 
decreased. 

It seems to me that there is another resemblance of some signi- 
ficance. Perceptions, as we observed, do not fade out altogether, 
they leave traces, which will be present in consciousness again 
through association, but which, of themselves, also possess a tendency, 
a certain potency to emerge. There is a continual competition among 
the subeonscious tendencies. Their potency varies with various 
conditions inter alia of novelty, emotionality, fortuitous associations. 
In ordinary circumstances there is an uninterrupted inhibition exerted 
by other ideas. When this inhibition is taken away, as is the case 
in dozing and during sleep, these subconscious ideas. may be present 
in consciousness again. This may be brought about by association, 
but surely their own energy may also co-operate. This appears from 
the difference in own energy appropriate to various ideas. For 
example: a personal name may recall the image of the person, but 
the latter does not always call up the name. An accident will be 
reproduced more readily when witnessed than when only read 
about. That own energy of ideas or perceptions to become central 
consciousnesses, which energy has been termed by Hrymans distance- 
energy, is utilized partly by obviating resistances and, when at the 
ingress into consciousness some energy is still left, this remainder 
is spent entirely in repulsing the resisting complexes of consciousness 
as far as possible into unconscionsness. These conditions occur with 
the just-mentioned retrograde amnesia, analogous phenomena of 
which are met with in the repulse of some reflexes by others, which 
lie still nearer to the threshold of consciousness. But Heymans also 
puts the case that there are hardly any resistances, so that there 
‘annot be any question about a loss of distance-energy through 
repulse. In such a case that energy will be applied in consciousness 
as energy of association, of sentiment, of thought and of will. Now, 
do similar manifestations also arise with subconscious phenomena? 
As regards some reflex manifestations, we are in a position to select 
such conditions as are perfectly similar to those required for the 
phenomena of consciousness, so that when they oceur there will be 
no resistances in their way. In this connection we may take it for 
granted, that knee-jerks are inhibited by simnitaneous centrifugal 
cerebral impulses. Affections of the pyramidal tract have disturbed 
the conduction of these impulses, so that the knee-jerks are no longer 
subject to inhibition. Well then, in these conditions many reflex- 
associations occur, viz. contraction of the adductors, and also frequently 
of the m. quadriceps of the other leg. 


433 


I annex a few other examples, the number of which may still 


be enlarged. 

It is known that the direction of voluntary thinking and acting 
is determined by the intentional idea in its after-effect. The bias of 
the mind arouses the most serviceable thoughts and motives; the 
others are inhibited. This is the course of every process of thought 
as well when we are simply designing a travelling plan, as when 
we are working out the most intricate scientific problem. The same 
holds also for mental development at large. From our earliest youth 
upwards there is an unconscious tendency by which the adult mind 
is developed from the simplest data. Physiologically we observe the 
same process, by which a single ovum develops into the full-grown 
body. In either case there is a tendency in the line determined by 
the result to be attained, i.e. the intentional idea. 

True, this result is not present in consciousness, but for the rest 
it is perfectly similar to the intentional idea in its secondary function, 
because either of them determines the developing process. 

In mental growth the innate tendency dictates a certain trend. 
Great disparities present themselves, e.g. in the types of observation 
and in individual character. Interest, which is chiefly innate, plays 
a prominent role in the formation of the types of observation. The 
visual type e.g. shows an affinity for sight-impressions, while it 
neglects the auditive-, and the motor impressions. In_ physical 
development we distinguish a similar difference in trend. The fertilized 
ovum cell is omnipotent. In it is hidden the power for development 
of all tissues. Differentiation of this potency appears after repeated 
division of the cell. Some cells can supply only epithelium, others 
only connective tissue, or muscular and bony tissue. 

From the facts above stated it appears that there is a far-reaching 
concordance between the laws of some psychological, and, let me 
put it cautiously, some physiological phenomena. Our results justify 
us in suspecting that with a fuller knowledge of both groups of 
phenomena a_ psychological equivalent may be found for every 


physiological phenomenon. 


28* 


Physics. “On the Separation of Gas Mixtures by Diffusion in a 
Flowmyg Gas’. By Dr. G. Hertz. (Communicated by Prof. 
P. EarenFEst.) 


(Communicated at the meeting of November 25, 1922). 


As is.well known, the differential equation: 4o—0O, in which @ 
represents the density of the diffusing gas, is valid for stationary 
phenomena of diffusion in media at rest. This equation does not 
contain the constant of diffusion of the diffusing gas at all. If, 
therefore, the diffusion of a gas mixture is considered, the ratio of 
the partial pressures of the components of the mixture is constant 
throughout the space, i.e. unmixing does not oceur with such a 
stationary diffusion phenomenon. This however, is different, as will 
be shown in what follows, with stationary phenomena of diffusion 
in a moving medium. As such a moving medium we take a flowing 
gas. Let the velocity of this gas medium be v, and let it satisfy the 
condition div » = 0. The constant of diffnsion of the diffusing gas 
under definite circumstances be 0, its density 9, which for the cal- 
culation we shall assume to be small compared with the density of © 
the gas medium. The quantity of the diffusing gas passing through 
the unit surface in the unit of time hence its current density, is equal 
(o the sum of the diffusion and the convection current; it is: 


i=—dJdgrade+ov 
For stationary phenomena divi 0, so that taking into account 


that div » =O, we get the following differential equation for such 
phenomena: 


1 
Ae= Fi (v, grad g) 


In contrast with the equation 4 9 =O holding for a medium at 
rest, this equation contains the constant of diffusion dé. Accordingly 
the distribution of the density in space is bere dependent upon the 
constant of diffusion. If, therefore, a gas mixture is made to diffuse 
in a stationary medium the ratio of the partial pressures is constant. 
On the other band this ratio is variable in a moving medium; and 
this brings about the possibility to use this phenomenon for the 
separation of gas mixtures. 


435 


In what follows two special cases will be treated, which it has 
been possible to realize experimentally, and which can be used for 
the separation of gas mixtures. In both cases a gas medium flowing 
with a constant velocity » is used, the direction of which will be 
chosen as direction of the negative z-axis. For this case the differ- 
ential equation is: 


When we assume 9 =o, for «=0, and 9 =0 for r=, we 
get as a first example the case of diffusion against the gas current. 
The solution is easily seen to be: 

va 
e=o¢ ° 

The density of the gas diffusing against the current decreases, 
therefore, according to an exponential function, the gradient of which 
depends on the ratio of the current velocity to the diffusion constant. 
When now a mixture of two gases whose partial pressures for «=O 
are 9, resp. 9’, diffuses against the current, the following equation 
is found for the ratio of their partial pressures as function of the 
place : 


This distribution agrees in form with the distribution of the partial 
pressures in the field of gravitation determined by the barometer 
: L ey 
formula, with the exception only that here the quantity 5 takes the 

C 
place of the specific gravity, and the whole pressure gradient can 
be brought about at a distance of the order of a millimeter. 

If this phenomenon is to be used for the separation of a mixture, 
the gas present at a certain place, e.g. at «= /, must be pumped 
oft. The limiting conditions then become e—o, for «=O and 
o =0 for x=1. The solution then becomes: 


in which C' is a constant. If, as in practice, e 5 is small compared 
with 1, C is approximatiely equal to 9,. We thus find for the 


1) Compare S. Hoist Weser, Handelingen van het 17e Nederlandsch Natuur- 
en Geneeskundig Congres, Leiden 1919. 


436 


current density of the diffusing gas, i.e. the quantity which diffuses 
per unit of time through the unit of crosssection against the current: 
vl 


HOLD Oe te 


If a mixture of two gases which at «—O have the densities 0, 
and o', diffuses, the ratio of the quantities of the two gases which 
diffuse per unit of time against the current is equal to: 


This quantity represents, therefore, the degree of unmixing reached 
in such a diffusion process; inversely the product v/ is determ- 
ined by the diffusion constants of the gases that are to be 
separated, and by the degree of unmixing required. In order to 
make the efficiency also as large as possible, v should be chosen 
as large as possible and in accordance with this 7 small, as follows 
from the equation of the current density. 

The second case, which in practice has been realized, is the 
following one: let again v be the constant velocity of the flowing 
gas, and let the direction of the current be that of the negative 
a-axis. At a certain point in this current we now admit the other 
gas. This gas will then be carried along with the current, and 
at the same time be scattered to all sides by diffusion. In this 
case the distribution of the diffusing gas is found by integration of 
the differential equation : 


with the limiting condition that at infinity the density of the diffusing 
gas must be zero. When the point where the gas enters the current, 
is chosen as origin of the system of coordinates, and the radius 
vector is called r, we find the solution: 


Curbs 

o—=2 0.2 
z 

> 


in which Cis a constant. The factor — represents diffusion in the 
' 


medium at rest, the exponential function which is due to the 
current, is of the same nature as in the first case; only instead of 


r+a 
2 


, we have here 


If, therefore, a gas mixture is introduced 


into the current, unmixing takes place in this case as well. Further 


437 


the same remarks are valid here as in the first case; thus it is 
also practical here to choose the current velocity great and geo- 
metrical dimensions small to render the quantity attained as great as 
possible. 

All these considerations have completely been confirmed by expe- 
riment. In order to effect the separation of gas mixtures by diffusion 
in a flowing gas in practice, it is first of all required that as a medium 
a gas be chosen that can be easily separated from the diffusing gases. 
This can be attained in a simple way by using a vapour as medium 
gas, which can be condensed after having passed the place where 
the diffusion is brought about. All the experiments made so far, 
were carried out with water vapour of 15 to 60 cm. pressure. 
The use of mercury vapour of lower pressure may, possibly, be still 
more efficient; this will be further investigated. 

The chief point in the construction of apparatus for 
carrying out the process described above, is the produc- 
tion of a constant vapour current. When a gas passes 
over a sufficient distance through a cylindrical tube, a 
current is obtained with parallel stream lines, but the 
velocity is not constant; it decreases from the axis 
towards the walls of the tube, as is represented in 

Fig. 1. fig. 1. It is, however, possible to get a current of constant 
velocity, though over a short distance only, when the gas passes 
throngh a wide tube with a suddenly decreasing diameter or when 
the gas escapes from a vessel through a small hole in the wall. 
When in this way the medium gas flows 


from a vessel A into a vessel B (tig. 2), \ 

and when the gas mixture that is to be — a 
separated, is admitted to the vessel b, the - +TH(E “- 
case of diffusion against the gas current is || Aa 
realized. The velocity of the current can 
then always be chosen such that only the Fig. 2. 
component of the gas mixture that diffuses more rapidly, diffuses 
against the current and reaches the vessel A, from which it can 
be pumped off together with part of the medium gas. 

This idea was carried out experimentally as follows: the water 
vapour generated ina vessel heated electrically, flows through S (tig. 3) 
into a tube closed at the bottom by a metal plate D of a thickness 
of 1 mm. This circular plate of a diameter of 28 m.m. has 30 
holes of 1 m.m., each, distributed uniformly over its surface. 
Through these holes the water vapour enters the vessel V’, the 
lower part of which is surrounded by a cooling jacket, so that 


| 8 


438 


the water vapour is condensed. The gas mixture to be separated is 
admitted through the tube G. A part of this mixture diffuses against 
the current through the holes in D; this part can be pumped off with 
part of the water vapour through the tube 
H. The temperature of the water in the 
cooling jacket must be regulated in such a 
way, that the sum of the partial pressure 
of the water vapour and the pressure of 
the gas mixture in the vessel V is exactly 
so much smaller than the pressure of the 
water vapour admitted through the tube, 
that the required current velocity is obtained. 
The appliances used to attain this regulation, 
will be discussed later. The method deseribed 
has so far been chiefly used to separate 
helium-neon mixtures, and has proved very 
satisfactory. Even, when the process of 
diffusion was executed only once, from such 
a mixture containing 30°/, helium, helium 
could be obtained, the purity of which was 
so great, that in a Geissler-tube at a pressure 
of 1 m.m. the neon-lines were not visible 
with an ordiuary spectros cope. Considering 
the exceedingly great spectral sensitiveness 
of Helium with regard to very small quan- 
tities of Neon, this shows already a very 
great degree of purity. 

Though the unmixing of the gas mixture 
Fig. 3. by diffusion against the gas current was 


actually as great as was to be expected according to theory, the 
quantities obtained remained below expectation. This may be ex- 
plained by considering, that in the method deseribed only part 
of the cross section of the vapour current is used, because the gas 
must diffuse from the outside into the jets that issue separately 
from each hole. In order to deal with greater quantities another 
apparatus appeared to be more suitable, working according to the 
second example discussed above. This second case is in so far 
much more easily realized, as it is not necessary here to keep the 
current velocity accurately constant. It is immediately seen that with 
a current as represented in fig. 1, also unmixing of a mixture is 
to be expected, when this mixture is introduced at a point in 
the axis of symmetry of the current. The principal part of the 


439 


apparatus is reproduced in fig. 4. The water vapour enters threugh 
the tube &, which is ground off at the end, so that the water vapour 
leaves the tube in acylindrical jet. The gas mixture enters through the 

3 tube G, ending in a capillary concentric with &, the 

end of which is in a plane with the endplane of R. 

Opposite the tube A at a distance of 3 mm. there 

is a tube D, the opening of which is formed by a 

circular sharp edge of a diameter of 6 mm., and 

manufactured from metal for the purpose. The outer 
part of the cylindrical jet coming from R is as it 
were peeled off by the sharp edge. With a suitable 
choice of the current velocity this outer part of the 
vapour current practically contains only the com- 
ponent of the mixture which diffiises more rapidly ; 
this component is separated from the water vapour 
by condensation, and collected in a vessel. By far the 
- greater part of the gas mixture admitted through G@ 
passes on through the tube Jf with the inner part 
Fig. 4. of the vapour current, is also freed of the water 
vapour by condensation, and again admitted through G by means 
of a circulation pump. 

If the apparatus is to work well it is chiefly necessary that the 
velocity of the current is accurately regulated, and besides it is 
practical to lead the condensed water vapour back; else the water 
‘in the heating vessel would diminish too rapidly. Fig. 5 represents 
the whole apparatus. In the glass vessel I”, which is 50 em. 
long and has a diameter of 10 cm. the water is heated electrically 
by means of a heating wire wound on a layer of asbestos. The 
pressure of the water vapour in this space can be determined by 
means of a thermometer 7’ suspended in the vapour. This water- 
vapour flows through a tube to a bulb 4, and from there to the 
tube R of the diffusion apparatus, while simultaneously the gas 
mixture to be separated, enters the tube G through a very narrow 
capillary tube. By the regulation of the pressure of the gas 
mixture before it enters the capillary tube, an accurate control of 
the velocity with which the mixture is admitted, is made possible. 
The two parts, into which the gas current is split up by D, 
pass on through the tubes H WM resp. and reach the condensation 
vessels C, and C,, which are provided with cooling jackets A, and 
K,. Here the water vapour is condensed, and the water runs back, 
to W as is seen in the tigure. The part separated by diffusion is 
collected in C,, and the rest of the gas mixtures in C,. Both 


440 


these parts tog ether with some water-vapour leave the appara- 
tus each through a very narrow 
capillary. The water vapour is 
removed by freezing it out. The 
separated part is received in a 
vessel, the rest of the gas mixture, 
however, is again led back to 
the apparatus by means of a 
circulation pump. 

The vapour current is con- 
troled by regulating the current 
in the heating spiral wound on 
W, and the temperatures in K, 
and ,. The latter is effected 
in such a way that the water 
flowing through the cooling 
jackets with acgurately con- 
stant velocity is beforehand led 
through a copper tube, surround- 
ed by a heating coil, so that 
the temperature of the water 


depends on the current passing 
through this heating coil. The 
check on the current velocity 
is made possible by the capil- 
laries between H and C,, and 
between W/ and C,, these causing 
a difference of pressure between 
W and C, resp. C, that isin direct 
ratio to the current velocity in H resp. J/. This difference of pressure 
can be measured by the difference of level between the condensed 
water in C, resp. C, and the water in IW. Neither the absolute 
value of the current velocity nor the temperature of the water 
in AK, and A, need be known; when the level of the water 
in the two tubes with regard to the level in W is such, that 
the unmixing of the gas mixture is satisfactory, the heating current 
need only be regulated so, that this position is maintained. 

It is not necessary to keep the temperature, and with it the 
density of the vapour, accurately constant, for both the current 
velocity corresponding to a given difference of pressure between the 
ends of the capillary tube, and the diffusion constants of the diffusing 
gases are approximately inversely proportional to the density of the 


441 


vapour; accordingly the relation - characteristic of the diffusion in 
a flowing gas is not affected by small fluctuations in the vapour 
density. In order to prevent condensation of the water vapour 
against the walls, the whole apparatus is enclosed in a box, in 
which the air is heated a few degrees above the temperature in WV. 

The same degree of the separation is obtained by the first and 
the second method. As regards the quantity obtained the second 
method however, is considerably better. Only when it is required to 
separate small quantities, the former method is preferable, as in 
the second method a certain minimum quantity is required for the 
circulation. 

It is of importance to consider whether our method of the diffusion 
in a gas current is more efficient with regard to the separation of 
isotopes than the methods used up to now. This new method is 
no doubt superior to the usual way of separation by diffusion. It 
is, however, possible, that when we apply this method to gases 
with diffusion-constants differing as little as they do for isotopes, 
small irregularities in the current may have much greater disturbing 
influence than in neon-helium mixtures. Nor can it, of course, 
be expected that a mixture of isotopes should be completely separated 
by a single process of diffusion, for such a process, supposing: it 
be possible in principle, would require a very long time, as can 
be calculated from the above given formulae. On the other hand, 
e.g. in neon, a change in the ratio of mixing of the isotopes of 
about 30°/, could be expected as the result of one process of 
diffusion, so that it might be expected that a fairly far advanced 
separation can be obtained after not too many repetitions. It is 
not our intention to use the apparatus described above for the 
separation of isotopes, as it must undoubtedly be possible to 
construct apparatus on the same principle, working considerably 
more rapidly. 

Eindhoven, 1922. Physical Laboratory of the 

“N.V. Philips’ Gloeilampenfabrieken.” 
(Philips Incandescent Lamp Works). 


Physics. — “On the Excitation and Lonization Potentials of Neon 
and Argon’. (Appendix). By Dr. G. Hertz. (Communicated 
by Prof. P. EHRENFEsT). 


(Communicated at the meeting of November 25, 1922). 


In the measurements of the excitation and ionization potentials 
of neon and argon discussed recently‘), the value of 20,45 Volts 
measured by Franck and Knippinc was used as the first excitation 
potential of helium, in order to determine the absolute value of 
these potentials. Since then Lyman’) succeeded in measuring the 
spectrum of Helinm in the extreme ultra-violet directly. It can be 
shown from his results, that the values found by Franck and KnNrppine 
for the eritical potentials of helium, like Horvron and Davigs’ values, 
which are in close agreement with them, are too high. As Franck *) 
shows by a comparison of the values measured optically and electri- 
cally, 19.75 Volts must now be taken to be the first excitation 
potential, which value is accurate within 0.1 Volt. In connection 
herewith the exeifation and ionization potentials of neon and argon, 
having been measured relatively to helium must also be diminished 
by 0.7 Volt so that the following values are obtained : 

Neon: Excitation potentials: 16.65 and 18.45 Volts. 

lonization potential : 21.5 Volts. 

Argon: Excitation potentials: 11.55; 13.0 and 14.0 Volts. 

lonization potential : 15.3 Volts. 

The conclusions relating to the optical spectrum are not affected 
by this correction, as only the potential differences are used for 
them. Only the term 0.5s., which corresponds to the normal state 
of the atom, must be diminished, and becomes 174000 + 1000 for 
neon, and 124000 + 1000 for argon. 


Eindhoven. Physical Laboratory of the 
N.V. Philips Gloetlampenfabrieken. 

1) These Proc. Vol. XXV N°. 5 and 6, p. 179. 

2) Tu. Lyman, Nature, 110, 278, 1922. 

3) J. Franck, Zeitschrift f. Phys. 11, 155, 1922. 


Physics. — “Further experiments with liquid helium. Q.. On the 
electric resistance of pure metals etc. X. Measurements con- 
cerning the electric resistance of thallium in the temperature 
field of liquid helium.” (Comm. N°. 160a from the Physical 
Laboratory at Leiden). By Prof. H. Kamuriinen Onnes and 
W. Toyn. 


(Communicated at the meeting of October 28, 1922). 


§ 1. Object of the research. Method of preparing the resistances. 
The place of thallium in the periodic system of elements, between 
the super-conducting metals mercury and lead, made it seem pro- 
bable that it would become super-conducting at helium temperatures. 

We had at our disposal only rods of thallium from Kantsaum'). 
From this Mr. P. J. v. pv. Baan, instrumentmaker of the Phys. 
Lab., extruded wires of 0.2 and 0.5 m.m. thickness; they were 
brigat at first, but quickly became tarnished and grey in colour. 
At the distance of a few c.m. from the ends of each wire a 
second short wire was melted on in a small gas-flame; during 
this process the thallium was protected from oxidation by a layer 
of melted candle grease. The wire was then wound bifilarly upon 
a porcelain tube with a double screw thread baked into it, (these 
tubes were made by the Kénigliche Porzellan-Manufaktur, Berlin and 
have been mentioned before in Comm. N°. 152c § 2) and then the 
four thallium ends were each soldered to a copper wire, previously 
attached to the tube. The resistance thus prepared was enclosed in 
a glass tube made by the chief glass blower of the Phys. Lab. Mr. O. 
KusskLrinG, in the following manner. The ends of this tube through 
which the copper wires protuded were platinised, coppered, provided 
with copper caps and sealed up (see also Comm. N°. 133d, p. 60). 
To remove the oxidation layer on the 7-wire the resistance was 
rinsed through the opening at the other end of the glass tube and 
dried by a moisture absorber and carbon tube; a tap attached 


') According to a letter from the firm the thallium contained the usual amount 
of lead; about other impurities nothing was said. The same letter said that the 
firm did not prepare any “extra” pure material. M. Levin (Z.S. f. An. Chem. 46 
(1905), p. 31) states that KaHLBAun-thallium contains 99,91°/, Tl, N. KuRNAKow, 
S. Zemozuzny and V. Tararin (ZS. f. An. Chem. 83 (1913), p. 200), only say 
that they used pure Tl from KaHLBAum. 


\ 


444 


to this end of the tube was then closed. By means of a Tépler 
pump and a suitable arrangement of glass connecting pieces the 
resistance was then twice rinsed with helium and finally helium to 
a pressure of 51 c.m. was admitted; after this the glass tube was 
sealed at the narrow part provided for the purpose. (For the final 
form see fig. 2 of Comm. N*. 1606.) In this way in Dee. 1916 
were prepared 77-VIII-1916, diameter 0.2 m.m. with a joint in 
the bifilar wire, and 77-IX-1916, diameter 0.5 m.m. 


§ 2. Zero determinations. For determining the zeros, the resistances 
71-V 111-1916 and 77-1X-1916 were placed in glass tubes filled with 
liquid parattin (owing to the war conditions no isopentane could be 
had) or with distilled benzine; the tubes were closed by corks, over 
which a layer of paraffin was laid. They were placed in ground ice, 
and the first measurement was made two hours later and repeated 
with intervals of about half-an-hour. The method of measuring used 
is either that of overlapping shunts in accordance with KonLrausca, 
or that of the compensation of the potential at the terminals of an 
unknown and a known resistance, connected in series, by means 
of a compensation apparatus free of thermo-forces in accordance 
with DuiusseLHorst and provided by O. Woxrr. Enclosing the wires 


TABLE I. 
Datum. Ti —VIII—1916. | Tl.—IX—1916. 
5 January 1917. | 1.149) QQ 
6 January 1917. 4.439 () 
Immersed in liquid air. 

8 January 1917. 4.4415 ¢) 

Immersed in Os, liq. and Hp liq. 
30 January 1917. 1.150, 
2 February 1917. 4.447, (2 
6 February 1917. 4.448 () 1.150; 
13 February 1919. 4.446 
19 February 1919. 4.446 
20 February 1919. : Vailas £0) 


eee 


445 


in an atmosphere of helium proved to be completely sufficient; 
the results of the zero point determinations are found in Table I 
(see p. 444). The zero point measurements are partly due to Dr. 
J. M. Bureers, now Professor at Delft. 


§ 3. Measurements in liquid helium; determination of the vanishing 
pomt temperature. The resistances were placed in the cryostat 
provided with a stirring apparatus shown in Comm. N°. 124c, 
fig. 4. For determining the amount of their resistance the second 
method mentioned in §¢ 2 was used. The measurements were 
always made with both directions of current in the circuit of the 
resistances, care being taken that to each of them the direction 
of the current in the compensation apparatus corresponded. More- 
over, in measurements below the vanishing point temperature the 
galvanometer was observed when the current was reversed in the 
circuit of the resistances only (this betrays super-conductivily more 
_ quickly): in the case of super-conductivity there must be no 
change of position observable. 

The temperatures are determined by the measurements of the 
vapour pressure of the helium bath, the connection between pressure 
and temperature having been derived graphically from the results 
in Comms. N°. 119 and N°. 1476. Close to the vanishing point 
temperature the pressure of the bath was followed with the katheto- 
meter (June 5 1919); we give below the diagram of a series 
of observations (in this field of temperature 1 m.m. pressure = about 
0.01 of a degree). 


aH 2 NN 
59,0mm! - S/S ; J 
. ; 10’ 20° 30’ 40 50 


Fig. 1. 


In spite of the fact that the wires were not in contact with the 
liquid helium, in the measurement of their resistances the galvano- 
meter reacted with surprising rapidity to the changes of tempe- 
rature of the bath. The results are given in Table II. 

From Table II it appears that a constant difference Aw exists for 
all temperatures; in spite of this additive resistance’) of 7/-V1I1-19/6 
with regard to 7’/-LX-1916 both become super-conducting at the same 


1) If this additive resistance is taken constant, it becomes 0,00083 W7,=0,003872; 
we must assume in the meantime that it is largely due to the joint. 


446 


[he behaviour of 77-VIII confirms the experience gained 


with Pb-wires (Comm. 


r 


temperat ure. 


« 
« 


3d § 15), that joints in a wire do not 
affect its becoming super-conducting. The unsteadiness of the resistance 


1 ¢ 


N*: 


is caused by the 


x. 


3 | 
range of 0.6 m.m. 


2°.3 


at 


pressure variations of the bath over 
Hg, corresponding to 0.006 of a degree; 


“ 


a 


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_*4000'0 0} Z00'0 0} 
9000'0 jnoge 561000 Wo. 2000'0 jnoge} °900°0 Woy 
S3UIMS SSUIMS SSUIMS SSUIMS (fer 2 €°6S 
&g °9000°0 §6100°0 °1000°0 9900°0 PES —'09 
2g 89000°0 °¢100'0 81000°0 *9900°0 cloned —*g¢9 
'g100°0 L900°0 ah’ —108 
2g 9000°0 '¢100°0 §1000°0 L900°0 66'S =a OS 
®g °L000°0 °g100°0 *3000°0 6900°0 sere 
*g000°0 *g000°0 89100°0 °6000°0 SL00°0 ve F 
00000" 1 00000°1 U 70cI'l | U 9Fb'b |°M60°ofLZ 
XTIL 9 y MAIL 9 | ‘SY “ur 
XPIL yy —WIAIL yy = mv ( a) — XI1Lm (= IATL | 916TXTIL yy | SOTITATL 4 | op [Boo] ul 
mM mM mnIPHy 
‘Tl ATAVL 


447 


in this field of temperature thallium is in the same condition as is 
shown for mereury in Comm. N°. 133a p. 24, fig. 6. At a current 


© TI Will. 7976. 
OTI. 1X .7976. 


© 


Fig. 2. 


strength of 3,1 m.A. through the resistances the resistance falls, thus, 
within a smaller temperature range than in mercury; a similar 
difference had been found earlier between mercury and tin.*) At 
T= 2°.32 K. all measurable resistance has disappeared. 


§ 4. Highest limit of a microresidual resistance. This limit is found 
from the quotient of the smallest observable potential difference and 
the threshold value of the current, it being assumed that Onm’s law 
still holds. We found: 


W 
—< 14.10~' at p=2.3 m.m. Hg and 


2730.1. 


W 
—<{ 24.10—1° at p=2.6 m.m. He. 


7 
AD MELAS 


The difference in the results may be due to the inequality of 
temperature, but more to the difference of current threshold value 


15 April 1919, for 77-VIII 


27 May 1919, for 7/-IX 


W 
of the two wires (see further§5). If the value Ws for thallium 
273°K. 


1) This comparison is defective, for as yet the fall of resistance in mercury, tin 
and thallium not has observed on wires of the same diameter by using the same 
strength of measuring current. [Note added in the translation.] 

29 

Proceedings Royal Acad. Amsterdam Vol. XXY. 


448 


is compared with that for other super-conductors (Comm. N°. 133d, 
p. 67) the retrogression of the limit. caused by a greater decrease 
of temperature below the vanishing point temperature would seem 
to be recognisable in the measurements of wires of different metals, 
as has been ascertained already by measurements of one wire of 
one metal. But we must point out that this general conelusion 
cannot be drawn before the value of the threshold current as a 
function of Tyanishing poin— 2’ aud of the dimensions of the wire 
is known and after it has been ascertained whether a returning 
resistance is due to a single ‘‘bad place’, or whether it is distributed 


over the whole length of the wire. 


§ 5. Threshold value. At some temperatures we tried to determine 
the treshold value of the current, that is the strength of the current 
sent through the wire, which again generates a measurable potential 
difference. The results are given in Table III. 

The two first observations in Table III show that for wires of 
different diameter at the same temperature the quantity = seems to 
be much more a constant than the current density. The latter 
quantity occurs in the expression for the magnetic field at the surface 
of the wire through which a current passes. 

F. B. Sitspew') drew special attention to the influence of this field. 
The determination of the threshold value of the magnetic field for 
thallium by means of external fields, and the comparison of it with 
H, derived from the two first observations in Table III] by means 


of Ha (the wires 77-VIIl and 77-IX therefore being regarded as 
straight), must prove whether these two strengths of field are equal, 
and that therefore the magnetic field is the primary factor in tbe 
disturbance of super-conductivity. Then the ‘‘bad places” referred to 
more than once, are the places with the smallest diameter; the returning 
of the resistance caused by the current, occurs first in these places 
only. The above mentioned experiment with thallium is prepared 
and also a similar one on a more extensive scale with the more 
easily manipulated tin; it must not be forgotten, that at the return 
of the resistance at great strengths of current such a development 
of heat soon takes place, that first the wire and if this melts the 
galvanometer is in danger; this makes the determination of large 


current threshold values rather risky. 
¢ 


1) F. B. Stuspee, Scient. Pap. Bur. of Stand. No. 307 (1917). 


449 


Fe 
Els = sO 1n, 16 
no tT = AN S 
c -_ ~ 
sin 
PHS KE 
c Un 
eked = ot nm N oO 
i % : 2 
eae eS Ss 
Sade SG GS 
OGeE 
uc 
<a 
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ee: eer olektast. GS 
QE 6» oN Oo = 
= — 
aut ise) Oo o i=) 
E> 
#- | ¥ 
sy a 0 
ae oo AAG 
ES = Nn AN AN 
ee 
a 
O . 
= 
ale? 3 
Ye) 
Ww = mo © +t 
= = ss . ic Was Eo) 
a 2° i Te 
< ae, Ae 10 
Ee a 
ec 
se js 8 
OE o = a a a 
vu 
Ley 
LE 
a “NN 19 
EE * A a a 
i o io) 
=— Fs 
aQ:-= 
e mc 
= 
= =o 
3 = 
_— — ' 
a2] = Se a a a 
n Le 
Syeda 
[os =) Ee 
a o& ror) 
Ss & = 
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= 
3 = > a 2 a 
3 
<= 5 
on > Yo) 
nN a 


1) The two first temperatures in this table are derived graphically by means of 
a formula slightly differing from that given in Comm. No. 159 in the ,Discussion”. 

*) Referring to § 3 concerning the heat conductivity of helium vapour, yet the 
threshold values might have been found greater, when the resistances would have 
been surrounded directly by liquid helium. [Note added in the translation). 


29* 


450 


If we assume, that in super-conduetivity the current runs only 
in an extremely thin layer at or along the surface of the wire 
and that each element of a section of this layer ceases to be super- 
conducting at a certain current saturation dependent upon the tem= 
perature, integration over the whole layer yields the threshold current 


: B) bsg ; 1 
and for wires of different diameter we get the constancy of —. 
- 


The assumption of current saturation along the surface does not, 
however, explain the connection, suggested by Susser, between the 
threshold values of the current and the magnetic field. 


Physics. — ‘Further experiments with liquid heliwm. R. On the 
electric resistance of pure metals ete. X1. Measurements con- 
cerning the electric resistance of ordinary lead and of uranium 
lead below 14° Kk.” (Comm. N°. 1606 from the Physical Labo- 
ratory at Leiden). By Prof. H. KamMeriincu OnneEs and W. Tvyn. 


(Communicated at the meeting of October 28, 1922.) 


§ 1. Object of the research. Method of preparing the resistances. 

In Comm. N°. 133d § 133 we reported that ‘“Kahlbaum’’ lead 
became superconducting at the boiling point of liquid helium, and 
remained so at 4,°3 K., the highest temperature attainable with the 
usual cryostat for liquid helium; in § 15 of the same Comm. from 
the threshold value of the current at 4,°25 K. the vanishing point 
temperature was estimated at about 6° K. The object of the invest- 
igation described below was to establish the vanishing point tempe- 
rature of lead more accurately, as well as to trace the difference 
in the vanishing point temperature of lead and uranium lead (Ra G) 
and to follow the course of the change in the resistance of lead 
with the temperature above the vanishing point, if possible up to 
14°,0 K, the lowest liquid hydrogen temperature. Regarding a possible 
difference of vanishing point temperature for isotopes it seemed not 
impossible that the occurrence of the superconductivity might be 
influenced by the mass of the nucleus. '). 

For the preparation of the resistances we used “Kahlbaum’’ lead 
and uranium lead (Ra G), of which Prof. Héxiescamip of Vienna 
very kindly put 16,5 gr. at our disposal; the atomic weight of 
ordinary lead from non-radio-active sources is 207,20, that of Ra G 
from BroéGcerrit used is 206,067). Wires were drawn from both kinds 
of lead and resistances prepared from them in the manner described 
in § 1 of Comm. N°. 1607; the chemical properties of the metal 


') Concerning the properties of isotopes see the article by K. Fasans in the 
Elster-Geitel-Festschrift (Vieweg) and the Presidential Address to the American 
Association at Ballimore, Dec. 1918 by T. W. RicHarps. 

2) According to a letter from the firm of May 17th, 1916, “Kahlbaum" lead 
contains a trace of Cu and Fe, the total impurity is less than 0,01°/); in a letter 
of Dec. 8th, 1916 they give a more precise calculation of impurity.: 0,002°/, Cu 
and Fe. For an account of the atomic weight of lead isotopes cf. F. W. Aston 
“Isotopes”, London 1922. 


452 


made it possible to extend less care on them than on the prepara- 
tion of the Tv-resistances, so that it is not necessary that the 
resistances should be shut off from the air in a glass tube with 
helium gas. We used the resistances ?b-1919-B, diameter 0,5 m.m. 
not enclosed in a helium atmosphere, Pb-1919-/, diameter 0,12 m.m. 
enclosed in a helium atmosphere and /sotope 
Pb-1919-/, in dimensions as much as possible 
the same as Pb-1919-/ and treated in the 
same way. 


§ 2. Arrangement of the cryostat. The eryostat 
with which the experiments were made, is 
executed by and under the supervision of the 
chief of the Techn. Dep. of the Cryog. Lab., 
Mr.G.J.Frim. Roughly speaking, it is the same 
as that described in Comm, N°. 1246. A charact- 
eristic of the present cryostat is that objects to 
be measured are surrounded by helium vapour 
or gas (the latter at very low temperature); by 
using it, the temperature field between the 
boiling point of helium (4°,2 K.) and the 
lowest temp. obtainable with liquid hydrogen 
(14°,0 K.) is bridged over for the first time. 
For the arrangement see fig. 1. In the entirely 
silvered vacuum glass A, an also entirely 
silvered vacuum glass 6 hangs in an inverted 
position, ending in a single silvered glass tube; 
the bell-shaped space inside this glass is the ex- 
perimental chamber, In this space are found the 
resistances (in fig. 1 there is only one, marked 
W) and the heliumgas-thermometer 7. The 
upper end of B opens out outside the eryostat 
and is connected with the gasholder; B is 
there provided with a regulating tap K for 
blowing off (not visible in ‘the drawing). The 
liquid helium comes in through the entrance 
D; the floater C shows the height of the 
helium level. If the tap A, leading to the 
gasholder, stands open, the helium will fill 
both A and B; at the beginning of the ex- 
periment measurements can thus be made 
Fig. 1. at the boiling point of liquid helium, If the 


453 


tap A is closed, the helium vapour formed will quickly drive the 
liquid helium out of the bell-shaped cryostat space; by opening the 
tap A and putting on the electric heating in the spiral /, a constant 
vapour stream may be sent through the cryostat; the stream may 
be brought to the temperature desired by electric heating of the 
spiral G; thus the liquid level of the evaporating helium remains 
between F’ and G. The copper mantle / inside the bell contributes to 
the acquiring of an even temperature over the whole space; further 
experiments must show in how far uniformity of temperature has 
been achieved with the arrangement as described. The first cooling 
uses a great deal of liquid helium. 


§ 3. Resistance and temperature determinations. 


The resistances are measured by comparison of the deflections of 
the galvanometer, when connected with the extremities of an unknown 
and a known resistance (0,001 or 0,01 2 O. Woxrr); the resistances 
are proportional to the means of the deflections for both directions 
of the current, as follows from the comparison of the deflections 
for 0,001 and 0,01 2. 

The temperatures are determined with a heliumgasthermometer 
of constant volume and with open manometer, the height of the 
barometer is read from an aneroid. In the measurements of May 
18" 1920 the zero pressure of the thermometer was calculated to 
be about 1140 c.m.; as it was not easy to determine this pressure 
accurately, the pressure at the temperature of liquid helium was 
taken as calibration point (this temperature followed from the vapour 
pressure of the bath). 

For the measurements of May 28*" 1920 the zero-pressure of the 
thermometer was decreased to 290 cm., in order to have less difficulty 
with the corrections on the provisional international Kelvin scale, 
these corrections in and below the field of liquid hydrogen being 
insufficiently known. As two calibration points the tensions of the 
thermometer served, placed in liquid helium (May 28 1920) and in 
liquid hydrogen (May 29 1920); the temperatures of these points 
again follow from the vapour pressure of the bath, using the data 
from Comm. N°. 1475 and N°. 15606. 

For the correction of the indications of the thermometer on the 
provisional international Kelvin scale, we had at our disposal the 
data of Comm. Suppl. N°. 34a, p. 17, note 4 (obtained from the 
data of Comm. N°. 102c), in which B _es4e¢, has been taken zero, 


454 


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may, according to calculation, be neglected even with a large density. 


455 


and also from Comm. N°. 119 §56 Byoosx. = — 0,000047 *); Table 
V of Comm. N°. 156a@ gives a resumé of the corrections, calculated 
with the above data. In accordance with note 1 and 3, p. 27, 
Comm. N°. 156a here B, = 0,000499, Byoo = 0,000476, «ine = 
= 0,0036614 are taken, and the influence of the C’s is neglected ’). 

New determinations, to be published shortly, of helium isotherms 
at 7’= 20°,5, 4°.2, 3°,7 and 3°,4 K. gave provisional new values 
for B, which therefore infer the introduction of different corrections 
in the provisional intern. Kelvin-scale; they are larger than those in 
Table V, Comm. N°. 156a and they do not come into line so well 
with those for higher temperatures. For the sake of completeness 
we give a comparison of these in Table 1. (ef. p. 387). 


§ 4. Temperature of the vanishing point. On May 18 and 28th 
1920 all three resistances proved superconducting in liquid helium 
and behaved, therefore, in the usual way. After this the cryostat 
was gradually brought to a higher temperature by electric heating 
of the vaporised helium. At a certain moment the galvanometer 
moved quickly over 35 ¢.m. on the seale and the vanishing point 
was apparently reached; the suddenness of the deflection speaks 
well for the usefulness of the cryostat if not too high demands are 
put upon it. A repetition of the heating (very gradually) confirmed 
the first result. While the temperature was kept constant the thermo- 
meter was read at the vanishing point. The results are given in Table III. 


TABLE Iil. 
Data. Filling. Peas thermom. in Te, uncorrected c t. 16, 
local m.m. Hg. 
: | 
May 18, 1920.| 1 263.6 6.25 0.58 6.8 K. 
| 

May 28, 1920.) II 73.9 a. 7.0g 0.15 a. 7.25 

BTM, 0.15 b. 7.25 


B 
1) The B= —- 0,000047 is that derived according to pv = RT + —; the B's 


= 
further mentioned in this number are those according to pry = rr(1 { = in 


agreement with the change of notation mentioned in note 360 of Comm. Suppl. N°. 23. 

2) These values for Bo, Bioo and ~;He must be retained to get the corrections 
on the provisional internat. Kelvin-scale. Measurements have sliown that it would 
have been more correct to use By=0,000513, Byy) = 0,000492 and x; He 
0,0086613 (Comm. N°. 102b, Table | and Com. N°. 156a, p. 22, note 1); this 
would lead to a second provisional intern. Kelvin-scale (helium-Avogadro-seale) for 
which reason we retain the first B's. 


456 


In filling Il @ is caleulated by interpolation between calibration 
points 20°24 and 4°07 K., 6 by using only the calibration point 
20°,24 K: in the same way as in filling I only calibration point 3°,60 K. 
needed to be used. 

The agreement between the measurements with filling I and II 
is bad. If in filling Il we caleulate, with the pressure increase 
of 10,3° mm. per degree, the temperature of the helium on May 
28, 1920, the calculation yields 4°,27 K, while the vapour pressure 
gave 4°,22 K (table Il); this is in favour of the measurements on 
May 28. If we further take the large Ads in filling I into 
consideration, a determination with filling I deserves less confidence 
than one with filling Il. We take T vanishing point lead = 7°,2 K, 
although it is still desirable to make a more accurate determination. 


§ 5. Comparison of the vanishing point temperatures of lead and 
uranium lead (Ra G). 

On May 18, 1920 the cross-thread of the kathetometer was 
adjusted to the mercury meniscus in the open tube of the thermo- 
meter at the pressure belonging to the vanishing point temperature 
of Pb-1919-/ (the meniseus in the closed tube must of course always 
be kept on the same mark). 

After a decrease of temperature /sotope Pb-1919-/ was inserted 
in the resistance circuit and the temperature again raised. If the 
galvanometer moved, because. the resistance passed through the 
vanishing point, the meniscus in the tube of the thermometer passed 
the cross thread; this phenomenon was ceriain up to 1 mm. He: 
“Kahlbaum”? lead, atomic weight 207,20 and wranium lead (Ra G), 
atomic weight 206,06 have the same vanishing point temperature within 
the accuracy of */,, degree. The same result was yielded by Pb-1919-B; 
an influence of the smaller current density in consequence of the 
larger diameter could not be detected (the strength of the measuring 
current was always 7,8 m.A.). 


§ 6. Resistances above the temperature of the vanishing point. 

The results of these measurements are given in fig. 2; the point 
most to the right, placed within a square, is the result of a mea- 
surement in liquid hydrogen. As vanishing point 7°,2 K was taken. 
To make the curve join on properly to the one in the field of liquid 
hydrogen it must be traced as in the diagram; that is why corres- 
pondence with the points marked is defective. The broken crosses 
have the following meaning: if the difference between the vanishing 


457 


point temperatures found on May 18 and May 28" may be 
attributed entirely to At having been taken too large on May 18", 
all the other temperatures must be recalculated, this recalenlation 
yields the crosses. Although this approximation is theoretically not 
quite correct, as 7’— At and not 7 ought to rise at every temperature 
in the same ratio, yet the results are in favour of the suggested 
assumption. 


65 70 90 ome (30 T 


iz. 2 
Fig. 2 


e Pb—1919—I, 

© Isotope Pb—1919—I, 18 May 1920. 
(-) Pb—1919—B, 

“e: Pb—1919—B, 28 May 1920. 


X Reduced observations : § 6. 


Chemistry. — ‘The Action of Sodiumamide on Pyridine, and 
some Properties of a-aminopyridine”. By J. P. Wipaur 
and Exisappra Dringemansn. (Communicated by Prof. A. F. 
HOLLEMAN). 


(Communicated at the meeting of December 30, 1922). 


Through TscnirscHiBaBin’s') beautiful researches @-aminopyridine 
has become easily accessible. This investigator found that sodium 
amide acts on pyridine as follows: 

C,H,N + NaNH, — C,H,N.NHNa + H,. 

On decomposition of the reaction product with water, aminopyridine 
and sodium hydroxide is formed. 

As we required this substance as starting material for synthetic 
investigations, we have applied the method of preparation found by 
TScHITSCHIBABIN. Though also in our experiments a-aminopyridine 
was formed as chief product, we found other substances than the 
Russian investigator among the by-products. 

We experienced that the action of sodium amide on pyridine can 
take place in different ways, dependent on the nature of the sodium 
amide preparation used. We have prepared sodium amide according 
to TirHeriey’s indication by the action of carefully dried ammonia 
on melted sodium at 350—400° C. The preparation obtained was 
a pure white, showed a crystalline fracture, and contained no free 
sodium. This preparation did not react with pyridine. A preparation 
prepared at 300°, reacted very slowly with pyridine. In this expe- 
riment very little @-amino pyridine was however, formed; further 
a little y-y-dipyridyl, and some other products, which we did not 
examine. 

A sodium amide preparation of KasiBaum, which was pretty 
impure, as it contained free sodium and also sodium hydroxide, 
acted vigorously on pyridine, as TscuiTscHipaBin states. Another 
preparation of KaAHLBAUM, which was apparently much purer, acted 
in exactly the same way. A mol. of pyridine is diluted with toluene, 
and this mixture is heated with a mol. of finely powdered sodium 
amide at 120—125° for seven hours. 


1) Journal de la Société Physico-Chimique Russe, 46, 1216 (1914). 
Chem. Zentral Blatt 1915. I. 1065 


459 


We have decomposed the reaction product with water according 
to TSCHITSCHIBABIN’s direction, dissolved it in ether, and distilled 
it at a pressure of 15 m.m. The bulk went over at 104—125°, 
and was almost pure aminopyridine in agreement with the records 
of the investigator mentioned. At 130—180° and 15 m.m. an oil 
distilled, which soon gets a dark colour when exposed to the air. 
After some time white erystals separated out of this oil. Recrystallized 
out of water these crystals became colourless, long needles melting 
at 73°. This substance is the hydrate of y-y-dipyridyl, which has 
already been described by Anprrson. After drying in a vacuum 
exsiccator we obtained the y-y-pyridyl itself, which melts at 112°. 
We identified this substance by analysis and by oxidation with 
potassium permanganate. We obtained white crystals melting at 
307°, which agrees with the melting-point of iso-nicotinic acid. On 
action of picric acid on y-y-dipyridyl, both dissolved in alcohol, 
we obtained a picrate crystallizing in fine yellow needles, and 
melting at 252°. As appears from analysis this picrate contains 1 
mol. of pieric acid to 1 mol. of y-y-dipyridy!. With anhydrous acetic 
acid and zine dust the y-y-dipyridyl gave the intensive violet colour 
reaction, which was lately described by Dimroru and Hrenp. 

There are still some more substances to be found in the oil that 
distilling at 130—180° and 15 m.m. pressure. After the bulk of 
the y-y-dipyridyl had been removed from this oil, we treated the 
liquid with hydrochloric acid. Two chlorides were then obtained, 
which both crystallized in white needles. After recrystallisation from 
diluted hydroebloric acid one melted at 115—116°; the second 
melted above 280°. The latter substance appeared to be the salt of 
y-y-dipyridy]. 

We have liberated the base from the chloride of 115—116°, and 
obtained white crystals melting at 94—95°. This melting-point agrees 
with the «-a-dipyridyl-amine (C,H,N.),NH, which was obtained by 
Sruinsduser and Drepotper') from a-chloro pyridine and «-amino 
pyridine by heating with barium oxide. 

The nitrogen percentage of our crystals, which melt at 94—95°, 
agrees with the value calculated for dipyridy! amine. 

TscuitscHIBaBIN says that this dipyridy] amine is formed through 
the action of two molecules of pyridine on 1 mol. of sodium amide, 
but does not yet describe the experiments from which this appears. 
When speaking of the action of 1 mol. of pyridine on 1 mol of 
sodium amide (the same way as we performed the reaction) Tscuir- 


1) Journ. f. prakt. Chem. 98, 393 (1916). 


460 


SCHIBABIN does not mention the dipyridyl amine. He prepared the 
dipyridylamine from «-chloorpyridine and @-aminopyridine by heating 
with zine chloride, and gives as meltingpoint 86—87°. 

We have prepared a picrate from the dipyridylamine, which melts 
at 227°. 

Our observations on the melting-points of dipyridylamine itself, 
on the salt with hydrochloric acid, and on the picrate of this base 
are in perfect harmony with SrrinHAusEr and Diepoiper’s records, 
so that we have no reason to doubt the identity of our preparation. 

The investigation of the components of the oil that goes over 
at 130—180° and 15 m.m. pressure, was not yet completed then, 
for a large part of this oil remained liquid after treatment with 
hydrochloric acid. We removed the hydrochloric acid from this 
liquid part, and then distilled the oil at ordinary pressure. We col- 
lected three fractions, viz. of 298—295°, of 295—300° and above 
300°. The first two fractions had a nitrogen percentage of 13.9°/,; 
the fraction above 300° had 16.4°/, of nitrogen. From this last 
fraction a little dipyridylamine was still deposited. The first two 
fractions were joined; this liquid appeared to be strongly unsaturated: 
it immediately decolours a solution of permanganate and soda at 
ordinary temperature. We have subjected part of this liquid to the 
oxidation with sodium permanganate in sulphurie acid solution. A 
white substance, which crystallized in white leaves and melted at 
74°, could be isolated. The nitrogen percentage of it was 8.0 °/,. 
This shows that it cannot be a dipyridylamine or a dipyridyl. 

Besides these crystals, a viscid liquid was obtained from the oxi- 
dation product. The investigation of these substances is being con- 
tinued, 

It appears from all this that on action of sodium amide on pyri- 
dine there are formed, besides aminopyridine, several other pyridine 
derivates, among which the y-y-dipyridyl seems to preponderate 
quantitatively. T'scuirscu1BaBin likewise observed by-produets in the 
reactionproduct which arises from sodium amide and_ pyridine. 
After the «-aminopyridine had been distilled off, he states that an 
oil went over which distilled at 120—180° and at 15—20 m.m., 
and besides a fraction that went over at 180—250° and 15—20 m.m. 

From the fraction of 120—180° crystals are deposited which, 
after recrystallisation from benzene, melted at 158°. TscurrscHiBABIN 
supposed these crystals to be y-aminopyridine, but he could not 
identify the substance for want of material. From the oil distilled 
at 180—250° this investigator isolated the «-a’ diaminopyridine; 
there were also other substances present, which he did not identify. 


461 


In many experiments we prepared some hundreds of grammes of 
amino pyridine; the reaction always proceeded as we described 
above. We never observed a substance with a melting-point of 158°; 
nor did we ever observe a diamino pyridine. 

Accordingly the action of sodium amide on pyridine can evidently 
give rise to the formation of different substances. We have not been 
able to find out why with some sodium amide preparations amino 
pyridine was not formed. Addition of small quantities of water or 
free sodium had no influence on this. We also caused sodium to 
act on a mixture of pyridine and toluene, both at the ordinary 
temperature and at the temperature of boiling. In this case there 
was formed a tough amorphous mass, insoluble in water and in 
organic solvents, soluble in acids. By extraction with ether we could 
isolate only a small quantity of y-¢-dipyridyl. This wesult is in 
accordance with the early experiments of ANDERSON. 

The formation of the important quantities of y-y-dipyridy] in our 
amidisation seems, therefore, not to be in connection with a possible 
percentage of sodium in the sodium amide preparation used. 

As amino pyridine seems comparable with aniline, we examined 
the action of oxidizers on this pyridine base. For so far as we know, 
nothing is known about this. 

Bichromate and diluted sulphuric acid change a diluted solution 
of amino pyridine only slowly at ordinary temperature. When the 
mixture is left standing for some days, the liquid gets dark. From 
this solution an amorphous green substance is isolated, insoluble in 
water, alcohol, and ether, soluble with emerald green colour in 
diluted hydrochloric acid. On evaporation of the hydrochloric acid 
an amorphous blue substance was left behind. At 90° the action 
of sulphuric acid and bichromate on amino pyridine takes place 
more violently; and amorphous products are also formed. In these 
experiments part of the amino pyridine however remained unchanged. 

The action of potassium bichromate in acid solution on this base 
takes place much less rapidly than in case of aniline. 

The action of potassium permanganate proceeds in an entirely 
different way. Amino pyridine is rapidly changed by permanganate 
in acid solution; after a few minutes all the permanganate has 
disappeared. When a diluted solution of amino pyridine is added 
to a diluted permanganate solution containing soda, a slow action 
takes place. When, however, first a neutral permanganate solution 
is added to a diluted solution of amino pyridine, and then a few 
drops of 10°/, sodium hydroxide, a change of colour is immediately 
seen. When we start from a 0.1°/, solution of amino pyridine, the 


462 


liquid first becomes dark violet, then pure blue, after a few minutes 
the colour has become emerald green. This green colour does not 
change again, when there is no excess of permanganate present. If 
the solution of the amino pyridine is somewhat more concentrated, 
the green colour at once sets in after a transient dark colouring. 

This reaction is characteristic of amino pyridine and very sensitive. 
In acetyl! amino pyridine this colour reaction does not set in at the 
ordinary temperature until after some hours, soon however on boiling. 

Whether the acetyl rest is split off primarily here, has not yet 
been examined. 

A more detailed account of the observations discussed briefly here 
will be published in the Recueil des Travaux chimiques. 


Physics. — “On Centres of Luminescence and Variations of the 
Gas Pressure in Spectrum Tubes at Electrical Discharges’ I1.*) 
By Dr. L. Hampureer. (Communicated by Prof. H. A. Lorentz). 


(Communicated at the meeting of October 28, 1922). 


§ 1. lntroduction. 

Experiments made by the author in 1916 showed that continuous 
eurrent-discharges when passing through not too rarefied gases, gave 
rise to differences of pressure, the value of which, with sufficient 
current densify can amount to thirty per cent of the total pressure. 
A first communication on this subject appeared in the author’s thesis 
for the doctorate in the beginning of July 19177%). In these investi- 
gations such variations of pressure were observed in numbers of 
gases of very different natures, as argon, neon, helium, nitrogen, 
hydrogen; it was found that the effects observed are very great in 
argon, hardly perceptible in hydrogen, and it was seen that the 
pressure effect must increase with the intensity of the current (loc. 
cit. p. 94), and with the root of the moleculair weight (loc. cit. p. 107). 

Four months after the publication of this Thesis for the Doctorate 
F. Skaupy*) published a sbort paper, in which he mentioned differences 
of pressure in continuous current discharges observed by him (only) 
in the case of noble gases; these differences of pressure were small 
compared with the effect found by us owing to the small current 
density applied by him. 

In April 1920 the author of this communication ') published some 
further theoretical views and quantitative calculations about the 
effects found, F. Skavupy confining himself in the course of the same 
year to some qualitative remarks‘), which indeed referred more to 
the phenomenon of electro-striction, which in our opinion can only 
play a subordinate part. 

Finally in the middle of 1922 there appeared a publication by 
A. Rirrenaver*®) on an important experimental investigation, in 


1) Cf. for 1: L. HamBurGer, These Proc. Vol. XXIII N°. 2 and 3, p. 379. 

2) L. HamBurGer, Thesis for the doctorate, Delft 1917. Cf. These Proce. 20, 
1048 (1917). Zeitschr. f. Wissensch. Phot., 18, 1 (19). 

8) F. Skaupy, Verh. d. Deutsch. Phys. Ges. 19, 264—’67. Nov. Heft, ‘17. 

4) F. Skaupy, Zeitschr. f. Physik 2, 215. Aug. Heft, ‘20. 

5) A. Riirrpnauwr, Zeitschr. f. Physik 10, 269—274 ('22). 

30 
Proceedings Royal Acad. Amsterdam. Vol. XXY. 


464 


which the variations of pressure of noble gases were subjected to 
a closer examination and the dependence of the effects found 
on different variables was given in an approximative “empirical” 
formula. 


§ 2. Purpose. 

After having thus established our priority, we set ourselves the 
task : 

1s'. to show that the experimental results obtained by A. Rét- 
TENAUER in his extension of the investigations on the pressure effect 
correspond to the theoretical formulae developed by us in J, in 
which also the practical part of Rivrenaurr’s empirical formula is 
included ; 

2d. to prove that serious objections may be raised against SKAUPY’s 
theoretical view of the pressure effect; 

37, to draw further conclusions from Riérrenaver’s important 
determinations, also in connection with our earlier data on this 
subject, and our objective, quantitative determinations on light 
emission in continuous current discharges in spectrum tubes likewise 
published in our Thesis. 


§°3. Formula for the calculation of the pressure-effect. 
ROTTENAUER gives the empirical formula: 
AIVM 1 
A pS SS 
Pie 
in which Ap represents the difference of pressure found, fa constant, 
A the current density, g the gradient of tension, J/ the molecular 
weight, p the total gas pressure, / the length of the pos. pile, Q 
its cross section. 

It is seen from this that Rérrrnaver finds experimentally that the 
pressure effect would be in inverse ratio to the total gas pressure ‘), 
whereas the author of this paper found — also experimentally — 
that with not too great variations of p, Ap varied little, if at all, 
with p.*) : 

How is this difference in result to be accounted for ? 


1) Which was, indeed, also mentioned by F. Skaupy in his first publication 
(1917). 

*) RiirreENAUER is erroneously of opinion that it would have been found both by 
me and by SkAupy that in argon the pressure effect is in inverse ratio to the 
gas pressure. It was on the contrary observed by us that within certain limits 
the pressure effect showed a very slight variability with regard to the gas pressure. 


465 


On comparison of Rérrenaver’s researches with ours it appears 
that we made use of comparatively narrow capillary tubes as circuit 
of the current, the German investigator on the other hand of com- 
paratively wide tubes. We derived, however, already before, that 
two different formulae must be valid for these cases, and this as a 
consequence of the fact that in the case of wide tubes the laws of 
PotsruitLe should be applied when taking the diffusion phenomena 
- into account, for narrow tubes those of Kxupsen-Lanemurr. For in 

AQ’) 
the first case the electric mass-transportation c, re may be put 


D* bee 
Creme (Pat— Px) M 


in the second ease to: 


oe Poe re ‘)) 
aay ar M 


In the first case the theoretical formula for the pressure effect — 


equal to: 


Laat Ty eae 
taking into account that (— —— for tudes with round cross-section 


4 
— is equal to: 
AQ | PM Se oe 
= =Apnp= —*_VY uM — Mi. . i 
Dae Py P=h ans h pO . (J) 
in the second case to: 
AO st a Age t/a * se 
DR = SS aS aa ee ee 
Pp ts a dD Ja al! D ( ) 


in which 
oe Cy oe Gy - 42 <  : 
ar ait Vian : fe. Vag a =a-(-) and a a es 
When on grounds to be given later, the gradient g is taken 
inversely proportional to a, we may write equations / and // as 
follows : 


a 
[a Sa AT ome oe 80.5) 
p 
resp. 


1) In which ¢, is a constant. Compare further Equation 9, p. 390, These Proc. 
XXIII, No.2 and 3. The factor Q has been introduced, because A now denotes 
current density, in our former paper current intensity. 

4) Compare Equation 3, p. 382, These Proc. XXIII, No. 2 and 3, 1920. 

3) Compare Equation 1, p. 382, loc. cit. 

*) These equations have been obtained from the Equations 1 and 3, p. 382, 
These Proc. XXIII, 2 and 3, after multiplication by 1/p. This has been done on 
the strength of what was said in footnote 3, p. 385 of our paper of 1920. 

30* 


las 
Ap=fAgp5VM . SN jie’ yetecouun an CR 


in which equation /// must be valid for tubes the diameter of 
which is large with respect to the free path of the corpuscles, which 
is actually the case in Rirrpnaver’s experiments. It is seen that 
equation /// is identical with Rirrenaver’s empirical approximative 
formula. 


§ 4. On the injluence of the potential gradient on the pressure effect. 

The “empirical” introduction of the potential gradient by Rirrrn- 
AUER in the pressure effect equation rests on the testing by three 
kinds of observations : 

a. the dependence of the observed values of the pressure effect 
on the potential gradient with one and the same current tube and 
the same gas with different current densities. 

6. the dependence when the diameter of the discharging tube is 
varied ; 

c. the dependence when the nature of the gas is changed. 

With reference to @ we must remark that a critical consideration 
of the values published by Rirrenaver shows that the variation of 
the gradient is irregular, and besides smaller than the deviation of 


the values found for foes interse, which values should be appro- 
ximately constant. Thus in table 4 p. 272 of Rirrmnaver’s publication 
the gradient for argon varies e.g. between 1,87 and 2,36, while the 

p&p 
Ag. lh M 
4,98. For the rest the uncertainty in the determinations of the 
gradient seems to have been considerable. Where in our Thesis the 
gradient decreased with increase of current density, it appears to 
increase in a slight degree in the investigations recorded by Rirrmny- 
AUER in table 3, whereas it decreased in a great degree in table 5. 
For this category of cases a constant value had, therefore, better 
be substituted for g, and the empirical formula becomes identical 
with our theoretical equation (Z). 

This is, therefore, in harmony with the statement expressed in 
our former publication (loc. cit. p. 390) that “in the case that the 
nature of the bearers is not modified” (bence for a definite gas) and 
“with not greatly varying tension” (potential gradient) a is a constant. 

With reference to case 6 we remark that the experimentally determ- 
ined influence of g is unmistakable. So far as the consequences of 


“constant value” as a maximum varies between 3,70 and 


467 


q for a definite gas are concerned, this influence is also theoretically 
comprehensible. lt already follows directly from the equation (4) of 
our former communication (I loe. cit. p. 384) which is based on 
the equation of motion of the electrically charged particles in the 
electric field, and from which appears the proportionality with the 
potential gradient V, provided the nature of the bearers undergo 
no change with V. 

Already for this reason we may express this also in the equation 
of the mass-transportation by the electric current: 
760 
P 


1 
mass-transportation = — Q.4A. . 2,32 10-4 *) 
a 


: Mag 1 
(equation (9) communication I), by replacing — there by a factor 
a 


bg, in which 6 is a constant for a definite gas. Hence ~ == OE 
ag = constant. ‘ 

Let us also try to derive this directly from the nature of the 
electric conduction, and at the same time ascertain from it whether 
or no 6 has the same value for different gases. We then remind 
the reader that equation (9) of communication I teaches us that the 


; 1 : 
pressure effect must be proportional to the part — of the conduction, 
a 


which takes place through ions charged with mass. This part is in 
direct ratio to the concentration of the ponderable ions. The problem 
may, therefore, be reduced to the question whether increase of g 
can cause increase of the concentration of the ions. In case of 
proportionality the equation ay = constant may then be applied. *) 

This relation will actually have validity for electropositive and 
noble gases, when J. Franck and G. Herrz’s*) elementary theory 
is adopted, according to which, as is known, perfectly elastic collis- 
ions between electron and atoms are assumed to take place, till — 
under influence of the electric field — the electron has passed over 
such a distance, and in this has obtained so much energy that its 
energy exceeds the value connected with the ionisation tension. The 
greater g, the shorter the time in which this value is obtained; the 

1) With regard to the factor Q in the numerator, see note 1, p. 468. 

*) We neglect the electrons liberated at the formation of the positive ions, sup- 
posing that within stationary conditions as many of these electrons are disappearing 
by recombination and formation of negative ions charged with mass. Additionally 
it may be remarked, that in the field of this investigation the number of ions 
compared with the number of free electrons is very small. 


We intend to deal within short time more fully with this part of the subject. 
3) J. Franck and G. Herrz. Verh. d. D. phys. Ges. 18, 218 (16). 


468 


number of ionisations per time-unit will be direetly proportional to g. 

Later Franck and Hertz’), just as C. D. Cai.p’), in connection 
with N. Bonr’s theory have assumed that unelastic collision can also 
already take place before the tension of ionisation has been reached, 
in which then removal of one of the electrons of the atom to a 
path lying more outward, takes place. On return to the normal 
path this energy- can then be emitted. Yet the result of the elementary 
theory will be approximated by three cases: 

I. Through absorption of the radiated energy by neighbouring 
atoms (COMPTON) °). 

II. By increase according in quanta of the energy of slow electrons 
on collision with dislocated atoms (‘collisions of the second kind” 
in the theory of O. Kiem and S. Rossenanp; ef. also § 5). 

Ill. (In a slight degree) through the renewed collision between 
dislocated atom and (rapid) electron, before the former has lost 
energy by radiation (K. J. vAN DER BiJL*) ). 

In agreement with our conclusion. from equation (4) communica- 
tion | it may therefore really be expected that in approximation the 
relation @.g = const. will hold for each of these gases separately, 
so long as the nature of the bearers is not subjected to any charac- 
teristic modification. For in this case the energy-compensation ensuing 
from I—iII will always be the same percentage. This compensation 
must, however, be very different for different gases. So that, the 
tensions of ionisation also being so greatly divergent, we are led to 
accept the obvious conclusion that the value of ag will be different 
for different (noble) gases. We shall revert to this when discussing c. 

That for the rest deviation is to be empirically observed ad 6 
between a calculation based on formula III and observation (chiefly 
as a consequence of errors of observation), may appear from the 
following example (argon); though formula III would lead us to 
expect that the value: 

re 255 

AgV M1 
would be constant, a consideration of the values published by Rir- 
TENAUER shows that in table 5 e.g. the “constant” which amounts 
to about 2,3.10-%, for one and the same noble gas in a definite 
case (in which the pressure varies from 0,5 to 0,64 mm., the current 
density from 1,49 to 1,21 A/em?*. and the bore of the tube from 


1) J. Franck and G. Hertz. Phys. Zeitschr. 20, 1383 (719). 

3) C. D. Cuiip. Phil. Mag. (6) 278 (14). Phys. Rev. (2) 15, 33 (’20). 
') K. T. Compton. Phys. Review (2) 15, 476, 1920. 

4) K. J. van DER Bru. Phys. Rev. 10, 546 (717). 


469 


2,01 em?. to 0,454 cm?.) shows the maximum deviation of 0,7 . 10—-°. 

In opposition to the fact of such a maximum deviation of about 
30°, it may be stated that the values of the tension gradient for 
one and the same gas in RirreNaver’s observations inter se are to 
each other as a maximum as | to 4. We therefore consider (see 
also our calculation for nitrogen p. 472 footnote) the effect of y 
exceeding the errors of observation to be present. 

We consider the fact of this theoretical and empirical determi- 
nation of the approximated proportionality of the pressure effect with 
Ag, hence with the added energy, of great importance. It is in perfect 
harmony with the proportionality of the light emission of the pos. 
pile with the added energy, which had been established by our 
objective measurements. We will presently come back to this point 
of simultaneous and quantitative parallelism. (See § 5). 

With respect to case c we already remarked that divergent values 
should be expected for ag resp. 6 for different gases. This is opposed 
to Rirrenacer’s view; for this investigator thinks — with reference 
to his empirical formule — to be allowed to consider the pressure 
effects comparable for different kinds of gases, and assumes / to 
have the same value for different gases. In our opinion the way in 
which Rérrenaver introduced g into the empirical formula of the 
pressure effect, cannot very well be accepted. He was in this 
evidently led by the results for argon and helium (table 4 of his 
communication); in fact we find here only a maximum deviation 
of about 15°/,*). Besides on the ground of the theoretical expectation, 
we have, however, reason to think here of chance, also on the 
ground of what follows. In the absence of determinations of the 
value of g, neon has not been taken for a comparison by RtrtENAvER 
in the corresponding calculated constants. For this purpose we can, 
however, derive with amply sufficient accuracy from the determi- 
nations of the terminal voltage communicated in our Thesis that 
under comparable circumstances the potential gradient in neon 
amounts to about 24 times that in argon’). When we, therefore, 


1) In Riirrenaver’s tabel 4 we find for helium and argon for the same tube 


A aLre . A 
a maximum deviation in the “constant” Ag VM’ which amounts to about 


4,6.10-5, of a value of 0,75 . 10-5 
(in which p varies from 0.618 to 0,776 m.m.) 
qees Al 2 Sele SO eet L-2iteamp)/c.m-3) 

2) In the derivation from the terminal voltage cathode- and anode gradient 
have been taken into account. That irregularities at the electrodes cannot play an 
important part in our case, appears among other things when also the ratio of 
the tension-gradients for argon and helium are derived from the terminal voltages; 


470 


place the values of Ap, A, and p found for neon (RbTTENAUER, 
table 1 of his publication) in his table 4, we can write g=5 for 
neon, g being put at 2,0 for argon. Then we find: 


TABLE A. 
Pa ees | pa 
Tube p Ap A g rar 105 = constant 
ind | 
IIL 24=*%60 Neon 0.776) |07026))) ol 13) 55s 1.33 
ME ="60 Argon 0.741 | 0.062 | 1.21 | 2.0 4.98 
Ill 4 = 60 Helium 0.785 | 0.079 | 1.13 | 9.67 4.73 


in other words the value of the ‘constant’ is from 300 to 400°/, 
higher for argon and helium than for neon. This shows in our 
opinion that it is injustifiable to put the pressure effects for different 
gases comparable on such a basis. 


Conclusion. It is necessary to replace Rirrenaurr’s empirical 
formula by the theoretical formula: 


AVM! AVMI 
-p (9) resp, Ap=fip= ee) 
p D 


in which y(g) represents a function of the tension gradient, which 
in definite regions can approximately assume the form 6g, in which 
b represents a constant the value of which is not the same for 


different gases. 


§ 5. Region of validity. 

We pointed in our previous communication that the phenomena 
in the path of the current are very complicated, and that our for- 
mulae are drawn up for more or less idealized cases. What makes 
A. Rirrenaver’s determinations also so interesting is that they were 
carried out with noble gases, in which the conditions in the path 
of the current are naturally much less complicated than in the 
multi-atomic not-noble gases. Besides this investigator used a very 
long and wide positive pile, which brings out the influence of what 
happens in the positive pile better. 

We mentioned already that in his second publication F. Skaupy 


then the ratio appears to agree with that which ensues from the values of the 
potential gradient as they have been measured by A. RiirrENAUER with the 
positive pile. 


471 


as appears from some remarks, was inclined to the belief that the 
pressure effect might be referred to the phenomena of electrostric- 
tion. On page 215 loc.cit. it says about this: ,,Im meiner schon 
erwahnten Arbeit iiber die Druckdifferenzen wurde gezeigt, dass 
bei Argonréhren innerhalb eines gewissen Druckgebietes (etwa 0,5 
bis 3mm. Hg) die sich bei einer gegebenen Stromstarke einstellende 
Druckdifferenz zwischen den Enden der 600 wm. langen, 0,8 cm. 
weiten Rolre umgekehrt proportional dem in der Roéhre berrschenden 
Druck war. Durch einen Irrtum wurde diese Beziehung fiir alle 
Edelgasse als giiltig angenommen und darauf eine Theorie der Er- 
scheinung gegriindet. Diese kann wohl nicht richtig sein, da die 
Beziehung nur fiir Argon in dem genannten Druckgebiet erfiillt ist, 
aber nicht z. B. fiir Neon oder Helium.” 

We point out, however, that A. Rérrenaver does not only find 
the dependence on p for argon, but also for the noble gases neon 
and helium, so that here no argument is present to induce us to 
look for the central point of the explanation of the phenomena in 
another region. We also remarked before that already in 1880 D. 
Bos') showed that the effects which can ensue from the electro- 
striction for gases, are exceedingly small. 

Besides, as we could show that the region covered by A. 
RUTTENAUER quantitatively continued that examined by us, if only 
the right laws of diffusion are applied for every region, the validity 
of our theoretical conception is confirmed for investigations in which 


TABLE B. 


Pip as| V3" to! 50 or icay 1 toi 40 
OZ03 tos) 2 oT cas, sll, to: 70 
On>eetomelicuor cay 1 to 8 
On66etoest2) or ca. 1 to 20 
0.6 to 45 Ore Cayo llentone7 5:2) 
4 to 40 orca, lito) “10 
5 to 60 Onmicale alto” 12 


~ ZR xrAVO 


') Diss. Groningen. 

2) That for the tension gradient in this record of the ratios also observations 
made on nitrogen, are included, may be justified thus. We published the following 
measurements already before: p,; = 1.18 mm. Hg. Terminal voltage 288 V. 
4=65 em. g, =3.15 mm... M, = 28, 4; = 12.7 Amp. cm.?, p) = 0.15 mm. 
Pz = 0.15, 15 = 5, gg = 3.15, My = 28, Ay =12 7. For nitrogen in uviol-glass with 
Q=3.15 m.m* there are known to the author (Tabel ©) the following three obser- 
vations of p in connection with the terminal voltage, from which we arrive at the 
bracketed values for the potential difference between the ends of the positive pile 


472 


the values of the different quantities, are as a maximum to each 
other in the ratio as recorded in table B. 

Continued experimental investigation on others than the examined 
gases but also on the latter themselves can, however, still reveal 
much. For all these investigations have been made within limits 
for which it may be assumed that the nature of the luminescent 
centres and of the current-conducting ions does not undergo any 
essential change. We pointed out before that it follows from the 
researches of J. Srark'), A. Weanerr and J. Franck?) that when 
p is sufficiently reduced, and gy sufficiently raised, the pressure-effect 
reverses it sign*). It may, however, also be questioned, what happens, 
when the nature of the discharge is maintained, but the current- 
density is greatly increased. We know only one indication of an 
essential change taking place in this case; already in I we expressed ‘) 
the desirability of examining by means of continued investigations 
of the pressure-effect, whether anything could be derived from this 


[by making by estimation, an approximate calculation of the cathode and anode 
gradient and the loss of potential between the electrodes end the entrances of 


TABLE C. 

p in mm. Hg Terminal voltage | Pot. diff. pos. column Thesis 
0.34 212 Volt (ca. 170 Volt) table 4 
1.19 288 =, (ca. 240 ,, ) 7 10 
2.38 350, (ca. 290 , ) ae! 


the capillary path of the current]. Extrapolating we then find for p=0.15: 
pot. gradient in the pos. pile: about 145 Volts. If in connection with this we 
assume the pot. gradient to be 3/; at 0.15 m.m. of that at p, =1.19 m.m. 


| hence 7 = =| and if we bear in mind that we must apply here the formula 
92 


NG f Ag 7 VI, the following formula would follow from this 


plana l, _ Me 6,5 


=—.-—-= — 
A Ps I; l, 3 5 
: ; re ONS anew 
the ratio measured on nitrogen being ang —= 23. 


More and more sharply defined measurements are very desirable also here. 

') J. Spark. Botrzmann-Festschrift 1904. 

2) A. WeuNELY and J. Franck. Verh. d. D. phys. Ges. 12, 444 (1910). 

*) For convenience sake we shall distinguish this as “negative” effect from the 
“positive” effect found by us. 

4) Communication | loe. cit. 1178. 


473 


about change of the luminescent cenires on the transition from the 
blue to the red argon-spectrum. On this head A. Rirrenavgr’s 
experiments give no decisive result, because the current-densities 
applied by this investigator, are too small. The author expresses 
the hope that — experimenting in this region being impossible to 
him for the present — this remark may induce others to undertake 
a further investigation. 


§ 6. Quantitative and Simultaneous Parallelism of Light Emission 
and Pressure Effect. 

We derived in our former publication that the pressnre-effects are 
chiefly due to the transportation of ions by the electric current (mass- 
transportation), which ions have originated at the impact between 
electrons and atoms. Where the extension of the experiments corro- 
borates our theoretical conception quantitatively, we think that itis 
not devoid of interest to remark here that the theory of quanta 
manifests its simultaneous and quantitative validity with respect to 
light emission and pressure effect by means of the positive pile. 

We have, indeed, to do here with two typical regions of the 
application of the theory of quanta: 

1. With light emission, the region of spectroscopy, in which the 
phenomena should be studied, which present themselves on the return 
of electrons from abnormal to less abnormal paths; 

2. With the region of the pressure effects, in which the collisions 
should be studied between electrons and atoms, the formation of ions, 
hence*) the passing of the atom-electrons fom normal to abnormal paths. 

As soon as the “bearers” change their character, both the character 
of the light emission and of the pressure effect changes. The latter 
may reverse its sign; as regards the light emission the change finds 
among others a pregnant expression in the law of displacement 
already cited in our previous paper. 

If on the other hand the electric conditions do not change 
characteristically, if the bearers continue to preserve the same 
character, our quantitative objective measurements of the light emission 
and our and Riérrenaurr’s manometric determinations of the pressure 
effect prove the s7multaneous quantitative proportionality of light- and 
pressure effect with the added energy. That the light emission does 
not change its character through increase of the added quantity of 
energy, was only what was to be expected according to the theory 
of quanta. Accordingly we consider particularly the fact that the 
same thing holds simultaneously for the pressure-effect, a contribution 


*) As far as the positive ions are concerned, 


474 


io our knowledge. We see tn this a confirmation of the view that 
the atoms both absorb and emit energy in quanta, at the same time 
an imteraction between the two. regions, which latter finds expression 
in a related region of investigation, among others in Krein and 
RosseLaNnv’s theory '). 

The well-known theoretical parallelism between these two regions 
and the simulfaneous parallelism between the observations on the 
pressure effects and the light emission which have now been expe- 
rimentally shown objectively, corroborate anew the close relation, 
the wnity between these two classes of phenomena. 


§ 7. Summary. 

1. Our priority with regard to the “positive” pressure effect is 
established. 

It is shown that A. Rirrenaver’s experimental investigations quan- 
titatively confirm the theoretical view and formulae about the pressure 
effect found by us, which we gave before. This establishes confirms 
for an extensive region of validity defined in § 5 that the pressure 
differences chiefly occur in consequence of mass-transportation by the 
electric current. 

2. It is desirable to replace the emperical formula given by 
A. Rirrenavgr for the pressure effect by two formulae derivable 
from the theory, dependent on the ratio between the free path of 
the corpuscles and the (round) diameter of the tube, viz.: 

AV MI AVMI 
Ap=f—— -#(9) resp... Ap=f—~—-9@) 
Dp p 
in which ~(g) represents a function of the potential gradient, which 
can assume approximately the form 6g in definite regions; in whieh 
6 represents a constant the value of which is different for different 


gases. 

3. It is shown that the opinion advanced by F. Skaupy that the 
pressure effect would be determined by the elastic electron impact, 
is untenable. 

4. The significance of the simultaneous parallelism of the quan- 
titatively and objectively measured light and pressure effects with 
regard to the theory of the quanta is pointed ont. It confirms that 
the atoms both emit and absorb energy in quanta. 

5. Attention is drawn to the desirability of extending the investi- 
gations, in particular also to argon. 

Dordrecht, October 11, 1922. 


‘yy KLetn en RosseLvanp. Zeitschr. f. Physik. 4, 46 (’21). 


Botany. — “On a new clinostat after pe Bourmr’. By Prof. 
Bo A. FC. Went. 


(Communicated at the meeting of December 30, 1922). 


It has been known to every botanist for more than 15 years, 
that the clinostats in present use are not satisfactory with regard 
to great precision. Already in 1907 van Harrevenp') made the 
errors of those instruments known to us ina detailed study. He him- 
seif constructed a much better clinostat, satisfying high requirements, 
but nevertheless introduced only in a few laboratories. This will be 
chiefly due to the great costs, unsurmountable for most laboratories. 

To the above tact it has been chiefly due, that Mr. P. A. DE 
Bourer, mechanic of the Botanical Laboratory at Utrecht, asked 
himself, whether it would not be possible to construct a much 
cheaper clinostat, nevertheless coming up to high requirements. 
Those considerations have led to the construction of anew clinostat, 
the description of which follows. 

Fig. 1 shows the clinostat in a more or less schematic way. 1 is 
a shuntmotor, running directly full speed, and connected by a belt 
3, with a flywheel 2, to the axis of which a pinion has been fixed. 
With the aid of cog-wheels its motion is transmitted to the proper 
clinostat 5. The axis of the fly-wheel turns on ball-bearings. Now 
the question is, to make this fly-wheel revolve exactly once a second ; 
this cannot be attained by altering the speed of the motor or by 
regulating the diameter of the grooved wheels because of a too 
great oscillation of the voltage of the town-plant. Neither does the 
motor run regularly with equal voltage; namely with excentric load. 
For this reason a different construction has been used here. 

Into the circuit + — of the motor a resistance 12 has been 
inserted in the form of a lamp, in consequence of which the fly- 
wheel runs a little too slowly, e.g. half a rotation a second. If 
however this resistance is put out of circuit, the fly-wheel revolves 
a little too fast, e.g.-two rotations a second. This putting out takes 


1) PH. vaN Harrevetp, Die Unzuliinglichkeit der heutigen Klinostaten fiir reiz- 
physiologische Untersuchungen. Recueil des Travaux botaniques néerlandais. II]. 
1907, p. 173. 


476 


place every second with the aid of the pendulum of a clock keeping 


exact time. 


Fig. 1. Sketch of the new clinostat; description in the text. 


At 6 we see an electro-magnet every second turning magnetic 
for an instant and attracting the spring-armature 7. The turning-over 
switch 8 is drawn to one side by the spring 9, in consequence 
of which the contact 10 is made. The current passes from + through 
the motor straight to contact 10, next through a part of the switeh 
8, through the spring 9 and finally to —; in this way the motor 
runs full speed. 

But on the fly-wheel a cam 11 has been fixed; this makes the 
switch 8 cateh behind the armature 7, in consequence of which the 
circuit is broken at 10. Then the current has to pass through the 
resistance and the motor runs slower. 

The final result is that the fly-wheel makes exactly one revolution 
a second. Even considerable oscillations of the voltage of the light 


477 


and power-station are of no consequence, the only resulf will be, 
that the cam 11 is a little more to the right or to the left at the 
moment, at which the second circuit is closed, so that only the ratio 
of the rapidly and slowly revolving parts of the axis of the fly-wheel 
may be altered every second. This is of no importance, because the 
axis of the clinostat revolves at a much slower rate and the movement 
is transmitted to this by means of the cog-wheels 4, ete. 

To the horizontal axis of the clinostat a conical cog-weel has 
been fixed, in which another conical cog-wheel catches, fastened to 
an adjustable axis 5. This latter axis has been fitted on in such a 
way, that it can revolve on the horizontal axis and can be fixed, 
while the rotatory movement is not impeded. This enables us to 
give the axis of the clinostat any desirable position. By fixing the 
adjustable axis and releasing the adjusting-apparatus, a rotation of the 
plant perpendicular to the horizontal axis may be obtained. This 
arrangement is shown in fig. 2; the adjustable axis is fastened with 
the screw A, the adjusting-apparatus with the handle B. 

Fig. 3 gives a backview of the whole apparatus, in which the 
arrangement of fig. 2 has not yet been fitted on. This figure shows, 
that the apparatus is comparatively small and may easily be removed 
by one person. The position of the axis too may be modified 
without any difficulty during the experiment. 

To the simple construction it is owing that the costs of purchase 
are considerably lower than of any other satisfactory clinostat. An 
objection is, that the motor keeps running throughout the experiment 
and therefore constantly uses current. But then the axis revolves 
with great power, so that considerable weights can be carried, while 
excentric loading that is rather considerable, does not cause any 
alteration in the regular running of the clinostat. 

In order to check the running of this clinostat and compare it 
with Prerrer’s and van HarreveLp’s clinostats, the recording- 
apparatus of the auxanometer of KONINGSBERGER ‘) was used. 

For this purpose electrodes were fixed to the axis of the 
clinostat either right opposite to each other or at an angle of 90°, 
in such a way, that after each full rotation of the axis, the top of 
such an electrode once made contact in a mercurydish and in this 
way a circuit was closed for a short moment. Closing that circuit 
caused a writing glass-pen to be stopped in its course and to be 


1) V. J. KoninasBerGer, A method of recording growth under various external 
influences. Proceedings Kon. Ak. v. Wet. Amsterdam. W. en Nat. Afd. XXX, 
6/7. 1921. 


478 


sent back to its starting-point, while a drum with paper, on which 
the recording occurred, was moved on 1.5 mm. 


Anant 


h 
AR IF Ra. 
hy 


(fr 


Fig. 2. Top of the clinostat-axis with conical wheels, as described 
in the text. 


The pen moves along the paper with a velocity of 1 mm. a 
second, writing a straight line. A number of parallel lines arises 
in this way, as shown in fig.4, drawn for so many seconds as the 
period amounts to, needed by the clinostat-axis to make a half or 
a quarter of a rotation. 

If therefore the clinostat runs regularly, these lines must be of 
equal length, or may differ one second at most, with respect to the 
point of time at which the contact with the mercury is made. 


In the figure something else has been recorded: every 6 minutes 


479 


a time-signal is given on a continuous line T. Of course the distance 
covered by the circumference of the clinostat-axis in successive 6 


Fig. 3. Backview of the whole clinostat. 


minutes must always be the same; so the distance between the 
time-signals must not vary with a good clinostat. 

Now the various clinostats were tested in two ways; partly 
without load, partly with an excentric load on the axis. This latter 
was done, because that very unequal load causes the greatest diffi- 
culties in practice, especially when in the dark plants have to be 
fixed on a clinostat, or when we have to try several times in order 
to get an exact centering, when meanwhile the plants have already 
been exposed to the unilateral influence of gravitation for a long 
time. Fig. 4 shows the results of those experiments. 

In 1 the behaviour of a clinostat of Prerrer is shown with an 
excentric load, amounting to 0,26 KG. when calculated on the axis. 

31 

Proceedings Royal Acad. Amsterdam, Vol. XXY. 


Fig. 4. 


Hi 


480 


ie 


‘si 


i 


Hy 


rs 


I. Clinostat of Prerrer. Records of half rotations. 
B is the excentric overload converted on the axis. At 4. this load 
was removed. Il. Clinostat of van HARREVELD. Record of 1/4 
rotations. B as above. At 4 this load was increased to 2 KG. at 
which the clinostat stopped; next the overload was removed. III. 
Clinostat of pe Bourpr. Record of half rotations. B. excentric over- 
load as above. In all 38 figures T is the time-line, checked every _ 
6 minutes. 


481 


It may be noticed how great the difference is between the two 
halves of the revolution, while this difference disappears beyond the 
arrow, indicating the moment at which the excentric load is removed. 


II refers to the clinostat of van Harretvep; here the excentric 
load was larger, 1.6 KG., calculated on the axis and there too 
irregularities appear, which are sometimes very considerable. The 
arrow indicates the moment at which the excentrie load was 
increased to 2 KG. The clinostat had come to a stop; this happened 
with a clock-weight of 13 KG. If a heavier weight had been 
chosen, the movement would of course have continued. After 
removing every excentric load, the running was perfectly regular, 
as appears from the rest of the figure. 


Il] shows the working of the clinostat pu Bourrmr with an excentric 
load of 26 KG. calculated on the axis. We see that notwithstanding 
this, it runs quite regularly, so that the superiority of this clinostat 
is perfectly clear from the figure. 

A contemplation of the time-signals T in the three parts of the 
figure will necessarily lead to the same conelusion; these time- 
signals gave a sign after every six minutes. 

Summarizing I arrive at the conclusion, that this elinostat is a 
great improvement on those hitherto used. Now that plant-physiology 
is developing more and more into an exact science, the old “a peu 
pres” methods will have to be left and therefore care should be 
taken that the instruments used come up to high requirements of 
precision. 

Utrecht, Botanical Laboratory, December 1922. 


Biochemistry. — ,,Concerning the Synthetic Action of Bacteria in 
the Pauneh of the Cow’. By Prof. B. Ssoutuma and J. E. van 
per Zanpe. (Communicated by Prof. H. ZwAaRDEMAKER). 


(Communicated at the meeting of December 30, 1922). 


The question whether bacterial processes occurring in the paunch 
of ruminants are significant for the metabolism of these amimals’), 
should be given more attention to than here to fore, since, by way of 
trial, ruminants are fed with urea, made from the nitrogen in the 
air. For the significance of the substitution of urea for protein in 
the animal’s diet depends to a great extent on the capacity of the 
bacteria of the paunch to synthesize from urea, in the presence of 
non-nitrogenous substances, the amino-acids which the higher animals 
are not able to build up. 

Tryptophane is one of the amino-acids indispensable to man and 
to the higher animals. It is highly improbable that mammals can 
synthesize tyrosine from non-aromatic substances. 

We have tried to ascertain whether these two substances can be 
built up by the bacteria occurring in the cow’s paunch, when, 
beyond ammonia no other source of nitrogen is present than urea, 
asparagin or aspartic acid. 

Our procedure was as follows: *) . 

Directly when the animal was killed, part of the contents of the 
paunch was brought to our Laboratory in a sterile bottle, fitted 
with a glass stopper’). 

With the help of a sterile wire a little of the paunch contents 
(i.e. of the turbid fluid after removal of the coarser particles) was 
transmitted to sterile nutrient solttions, contained in Erlenmeyer- 
flasks plugged with cotton-cool, and which were of a depth of 1 


1) Here we refer to the development of volatile acids in the paunch from sugar, 
as demonstrated before by one of us (B. S.). See Bericht II] 5th International. 
Congres fiir “angewandte Chemie’’ Berlin 1903, p. 825. 

*) It was adopted because bacterial growth could not easily be recognized 
directly in the turbid juice of the paunch (even when much diluted), and also 
because we wanted quantitative data regarding tryptophane-formation. 

3) We would here gratefully acknowledge our thanks to Mr. HorrnaGet and to 
Mr. pe Graar, respectively director and sub-director of the Utrecht abattoir, for 
their kind assistance in obtaining the material required for these experiments. 


483 


to 1'/, em. The flasks were then left standing in an_ incubator 
at 36° C. Duplicate cultures were made for each experiment. 

When the bacteria were fairly developed (which was the case 
after two days) one of the cultures was examined for the presence 
of the amino-acids, alluded to above; the other remained in the 
neubator. Moreover a new culture-medium was inoculated with it. 
We used Uscninsky’s solution, unmodified or modified as indicated 
below. *) 

Since the py of the paunch contents was about 7,4, we took 
care to let the py of our culture media be the same. 

In order to demonstrate the presence of tryptophane we applied 
the reactions of Voisenut (with HCl, formaldehyde and nitrite) and 
of Hopkins-Cone (with H,SO, and glyoxylic acid). Minnon’s reagent 
was used for ascertaining the presence of tyrosine. VoIseNET’s rea- 
gent stains differently with indole and with tryptophane. Indole after 
shaking out with ether was reacted on with dimethylpara amidoben- 
zaldehy de. 

Uscuinski’s’ solution, whether modified or not, but invariably 
without an aromatic or heterocyclic compound, inoculated with a 
small quantum of the paunch-contents, always gave in the sediment 
(obtained by centrifugation after the addition of alcohol) after a 
sojourn at 36° C. in an incubator, a very distinct tryptophane, and 
tyrosine-reaction, whereas initially the reactions were negative. 

A better growth and more powerful reactions were obtained by 
mixing 10 c.c. of the fresh paunch fluid with 25 ¢.e. of Uscninski’s 
solution. 

Whereas the reactions in the sediment were invariably positive, 
the supernatant fluid displayed negative reactions. 

In order to make sure that the tryptophane and the tyrosine 
reactions were not due to other indole or phenol-derivatives, the 
sediment was, in a few cases, centrifuged anew with diluted alcohol 
and once more with ether (indole). The reactions of the sediment 
were as distinct as before. The cultures themselves were also shaken 
out with ether some times. With the above-named aromatic 
aldehyde the ether gave a negative indole-reaction. It was evident, 
therefore, that neither free tryptophane, nor other free indole-deriva- 
tives, nor free phenol-like bodies were present. The positive reactions 
may, therefore, be attributed to the body-protein of the bacteria. 

On inoculation of new Uscuinsky solutions with the cultures an 


1) The ordinary Uscuinsky-solution contains K, Na, Ca, Mg, PO,, Cl and SOQ,; 
besides glycerol, ammonium-lactate and sodium aspartate. 


454 


excellent growth could be noted, and after a couple of days positive 
tryptophane, and tyrosine-reactions of the sediment. 

The present investigation, therefore, shows clearly that there are 
bacteria in the paunch of the cow, capable of building up trypto- 
phane and tyrosine with an aliphatic nitrogen-compound and with 
ammonia. With every one of the six paunches we succeeded in 
obtaining this result. 

We consider the presence of tyrosine to be established when 
bacterial bodies show a phenol-reaction (Mi.Lon’s) The non-specificity 
of the tryptophane reactions is of no importance in our experiments. 
They are only needed to show the presence of an indole-derivative so 
long as tryptophane is considered as sole indole-derivative in the 
protein-molecule '). 

Positive results were also obtained in the experiments in which 
asparagin (or sodium-aspartate) had been replaced by urea. The 
bacterial growth was, however, decidedly slower. The ammonium- 
lactate had been substituted in these experiments by potassium 
lactate, so that urea was the sole source of nitrogen. 

After 2 24 hours the tryptophane-reactions were as a rule weak 
in the turbid culture solution and very clear in the sediment, whieh 
had been obtained through centrifugation. 

A couple of times we added tryptophane to the Uscninsky solution 
which resulted in the formation of indole contrary to the other 
experiments. 

Direct addition of indole inhibited bacterial growth considerably ; 
it was arrested completely by 50 mgms per 100 c.c. 

Whether tryptophane can be developed from indole, as assumed 
by Loeiz, is not borne out by the present experiments, for, where 
addition of a small quantity of indole caused some bacterial growth, 
the formation of tryptophane may have resulted from the presence 
of ammonium-nitrogen or asparagine-nitrogen. 

When substituting glucose for the glycerol and the lactic acid of 
the Uscuinsky-solution a tryptophane synthesis takes place which is 
almost equal to that in the ordinary Uscninsky-solution. 

In experiments under approximately anaérobic conditions the growth 
was inferior to that obtained in the manner above-deseribed. An 
experiment, in which air was drawn through the fluid by suction, 
did not yield a larger growth than usual. 


1) Since gelatine does not yield Vortsener’s, nor Mitton’s reaction and proline 
and oxyproline are contained in it, it follows that these two amino-acids do not 
give these reactions. 


485 


The histidine reactions thus far obtained, were still somewhat 
doubtful. 

Several microscopic preparations were made of the cultures. Some- 
times different species were present, i.e. diplococei, rod-shaped bac- 
teria; sometimes staphylococci and streptococci; in one case the 
predominance of one species was such as to render it difficult to 
find another. These almost pure cultures were not always made up 
of the same bacteria; sometimes they were small ovoid, at other 
times rod-shaped bacteria. 

It being known that even various stocks of one and the same 
species may differ largely as to the chemical changes they engender, 
we did not ascertain whether the developing species were in any 
way concerned in the result of the reaction. 

According to an approximate quantitative determination in a 
culture, three days old, the sediment of 100 ce. contained about 
3 mgms of tryptophane, i.e. per Liter 30 mgms, or 3 grms per 
100 L. (putting the paunch contents at 100 L.). 

A man of 70 k.g. weight requires per day about 2'/,—3 grms 
of tryptophane. Assuming the same ratio for a cow, this animal 
would require per day about 17'/,—20 germs. The quantity necessary 
for the producton of milk has not been taken into account here. 

Putting the tryptophane content of milk per L. at about 750 mgms, 
and putting the daily flow of milk at, say, 12 Liters, the animal 
would have to take in another quantum of 9 grms of tryptophane. 

As far as we are aware tryptophane synthesis by bacteria (B. 
coli and B. FrmepiAnper) from ammoniae and aliphatic nitrogen- 
compounds, has been demonstrated only once, viz. by Logig’). 

From the publication of Braun and Cann—Bronner’), which came 
to our notice when our experiments had nearly come to an end, 
it may be inferred that their experiments also pointed to trypto- 
phane synthesis, for they could grow coli, paratyphoid-, and Frirp- 
LANDER-bacteria when ammonia nitrogen was the only source of 
nitrogen present. Where they report, that under perfectly anaérobic 
conditions ammoniac-assimilation is impossible, even after the supply 
of more energy, the question rises (granting their theory to hold 
generally) whether in the rumination process an aérobic condition. 
exists which allows any synthesis worth mentioning. 

It may rationally be supposed that, wherever micro-organisms 
manage to live on inorganic or aliphatic nitrogen-sources, they them- 


1) J. of Pathol. and Bact. Bd. 23, 224 (1919/1920). 
2) Biochem. Zeitschrift Bd. 131, 272 (1922). 


486 


selves derive the cyclic amino-acids from these sources, it being a 
faet that protein, containing these amino-acids, is always present in 
these organisms. 

In how far the amino-acids, formed in the paunch, are of use 
to the metabolism of ruminants, will have to be made out by food- 
experiments, which will also have to show whether the bacterial 
protein, formed in the paunch, is resorbed. 

Let it be observed that we have never succeeded in demonstrating 
tryptophane (or tyrosine) in the fresh turbid paunch-fluid (after the 
removal of the solid particles) and also that we were not more 
successful in this respect after cultivating for some days in the 
incubator, either under aérobic or anaérobie conditions. 

Meanwhile we should not omit stating that reactions in a fluid 
like the paunch-fluid, are far less sensitive than those in unstained 
solutions. Only when 7 mgms of tryptophane per 100 cc. was added 
in the form of protein (bloodplasma) a perfectly distinet try ptophane- 
reaction was recognizable. 

Still, the phenomenon, just alluded to, does not point to an abund- 
ant tryptophane formation in the paunch, which is the more 
striking since the paunch fluid with Uscuinsky’s solution (10: 25) 
yields negative results at starting, but exhibits distinct reactions 
after 2X 24 hrs. 


The above experiments show: 1°. that various bacteria present in 
the paunch of cows can build up the amino-acids tryptophane and 
tyrosine from ammonia nitrogen plus asparagine (or aspartic) nitrogen, 
and also from urea as nitrogen-source. 

2°. that these bacteria can form quantities of tryptophane in the 
culture-medium of Uscuinsky, which may be of some significance 
for the metabolism in cows; however it is not quite certain whether 
this synthesis is equally intense in the paunch. 


(From the Chem. Labor. of the Utrecht Veterinary Univ.) 


CONTENTS: 


ALPHA-AUTOMATICITY (On the) of the autonomous organs. 152. 
AMYLASE of Aspergillus niger (The influence of hydrogen ion concentration 
upon the action of the). 6. 
ANAPHYLAXIS (Experiments on) with azoproteins. 34. 
ANTILLES (Cuba, the) and the Southern Moluccas. 263. 
ANTIPHOTOTROPIC CURVATURES (Further researches on the) occurring in the 
coleoptiles of Avena. 158. 
ARGON (A connection between the spectra of ionized potassium and). I. 67. 
— (On the mean free path of slow electrons in neon and). 90. 
— (On the excitation and ionization potentials of neon and). 179. Appen- 
dix. 442. 
ARSENIC (Determination of the vapour pressure of metallic). 387. 
ASPERGILLUS NIGER (The influence of hydrogen ion concentration upon the 
action of the amylase of). 6. 
Atom (On WHIT7AKER’S quantum mechanism in the). 414. 
AXES OF ROTATION of quadratic surfaces through 4 given points. 52. 
— and planes of symmetry of quadratic surfaces of revolution through 5, 
6 and 7 given points. 61. 
AZOPROTEINS (Experiments on anaphylaxis with). 34. 
BACILLUS POLYMYXA (On). 279. 
Backer (H. J.). The dissociation constants of sulphonacetic and ~ sul- 
phonpropionic acids. 359. 
Bacteria (Concerning the synthetic action of) in the paunch of the cow. 482. 
BACTERIOPHAGUS Of D’HERELLE (Studies on the). 31. IJ. 87. Ill. 171. 
BAUMSTAMM (Ueber einen fossilen) von Bolang (Java), ein Beitrag zur Kennt- 
nis der fossilen Flora Niederlandisch-Indiens. 9. 
BENDING-POINTS (Abnormal strikes near the) of the horizontal projection of 
‘ the geanticlinal axis. 327. 
BEWERINCK (M. W.) and L. E. DEN DoorEN DE JonG. On bacillus poly- 
myxa. 279. 
BiscouMaRIc AciDs (The). 175. 
BLoop (An objective method for determining the coagulation-time of). 127. 
BLoopveEssELs (On the significance of calcium- and potassiumions for the 
artificial oedema and for the lumen of the). 145. 
Boeke (J.). On the regeneration of sensitive end-corpuscles after section 
of the nerve. 319. 


w 
to 


Proceedings Royal Acad. Amsterdam. Vol. XXV. 


vat CAOPN SLE News 


BOESEKEN (J.). The dislocation theory of catalysis. 210. 
Bo tk (L.). On the significance of the supra-orbital ridges in the primates. 16. 
— The problem of orthognathism. 371. 

Bouter (De) (On a new clinostat after). 475. 

BRAIN (Phylogenetic and ontogenetic increase of the volume of the) in 
vertebrata. 230. 

Breit (G.) and P. EHrReENfest. A remarkable case of quantization. 2. 

— Calculations of the effective permeability and dielectric constant of a 
powder. 293. 

BREMEKAMP (C. E. B.). Further researches on the antiphototropic curva- 
tures occurring in the coleoptiles of Avena. 158. 

BROUWER (H.A.). Fractures and faults near the surface of moving geanti- 
clines. IJ. Abnormal strikes near the bendingpoints of the horizontal 
projection of the geanticlinal axis. 327. 

Bura (J. H. N. van bDER) and P. vAN RoOmMBURGH. Cyclic derivatives of 
mannitol. 335. y 

BuWTENDUK (F. J. J.). A contribution to the physiology of the electrical 
organ of Torpedo. 131. 

BuvoetT (J. M.) and A. Karssen. Research by means of Réntgen-rays on 
the structure of the crystals of lithium and some of its compounds 
with light elements. II. Lithium-hydride. 27. 

CALCIUM- and potassiumions (On the significance of) for the artificial oedema 
and for the lumen of the bloodvessels. 145. 

CaLcIuM ouTPUT (On the influence of the compositon of the food on the). 395. 

CaTALysis (The dislocation theory of). 210. 

— (Heterogeneous) and the orientation of adsorbed molecules. 324. 

CaTaLyst (The influence of a) on the thermodynamic quantities regulating 
the velocity of a reaction. 199. 

Cuinostat (On a new) after DE BouTER. 475. 

COAGULATION-TIME of blood (An objective method for determining the). 127. 

CoLeoptTiLtes of Avena (Further researches on the antiphototropic curva- 
tures occurring in the). 158. 

CONGRUENCE OF RAYS (Representation of a bilinear congruence of twisted 
cubics on a bilinear). 22. . 

CrystTaLs (Research by means of RO6ntgen-rays on the structure of the) of 
lithium and some of its compounds with light elements. II. Lithium- 
hydride. 27. 

— (Explanation of some interference-curves of uni-axial and bi-axial) by 
superposition of elliptic pencils. III. 81. 
CRYSTAL STRUCTURE (The) of germanium. 125. 


Cusa, the Antilles and the Southern Moluccas. 263. 


GFOSNEIDSEN TS Il 


CurvatTures (Further researches on the antiphototropic) occurring in the 
coleoptiles of Avena. 158. 

CYCLIC DERIVATIVES of mannitol. 335. 

Dik (H. W. J.) and P. Zeeman. A connection between the spectra of 
ionized potassium and argon. I. 67. 

DINGEMANSE (ELISABETH) and J. P. Wipaut. The action of sodium- 
amide on pyridine, and some properties of ~-aminopyridine. 458. 

DisLOCATION THEORY (The) of catalysis. 210. 

DissOCIATION CONSTANTS (The) of sulphonacetic and ~-sulphonpropionic 
acids. 359. 

DOOREN DE JOnG (L. E. DEN) v. Jone {L. E. DEN DOOREN DE). 

Dusois (EuG.). Phylogenetic and ontogenetic increase of the volume of 
the brain in vertebrata. 230. 

Duin (C. F. van) and H. R. Kruut. Heterogeneous catalysis and the 
orientation of adsorbed molecules. 324. 

EHRENFEST (P.) and G. Breit. A remarkable case of quantization. 2. 

ELECTRIC RESISTANCE (On the) of pure metals etc. X. Measurements con- 
cerning the electric resistance of thallium in the temperature field of 
liquid helium. 443. XI. Measurements concerning the electric resistance 
of ordinary lead and of uranium lead below 14° K. 451. 

ELectrons (On the mean free path of slow) in neon and argon. 90. 

ELuiptic PENCILS (Explanation of some interference-curves of uni-axial and 
bi-axial crystals by superposition of). III. 81. 

EMiGRATION (On the causes of the) of leukocytes. 36. 

ENpD-coRPUSCLES (On the regeneration of sensitive) after section of the 
nerve. 319. 

Eouivisria (In-, mono- and divariant). XXII. 341. 

EXCITATION POTENTIALS (On the) and ionization potentials of neon and 
argon. 179. Appendix. 442. 

FerINGA (K.J.). On the causes of the emigration of leukocytes. 36. 

Fora (Ueber einen fossilen Baumstamm von Bolang (Java), ein Beitrag zur 
Kenntnis der fossilen) Niederlandisch-Indiens. 9. 

FORMENKOEFFIZIENTEN (Ueber Determinanten aus). 354. 

FRoG-MUSCLE (On the progress of the veratrin-poisoning of the striated). 364. 

Funke (G. L.). The influence of hydrogen ion concentration upon the 
action of the amylase of Aspergillus niger. 6. 

GALVANOGRAM of man (On respiratory oscillations in the). 225. 

Gas mixtures (On the separation of) by diffusion in a flowing gas. 434. 

GAs PRESSURE (On centres of luminescence and variations of the) in spectrum 


tubes at electrical discharges. II. 463. 


IV CONTENTS 


GEANTICLINES (Fractures and faults near the surface of moving). II. Abnor- 
mal strikes near the bending-points of the horizontal projection of the 
geanticlinal axis. 327. 

Geometry (A new method for the solution of the problem of the character- 
istics in the enumerative). 113. 

GERMANIUM (The crystal structure of). 125. 

Griaas (R. F.). Observations on the incandescent sand flow of the valley 
of ten thousand smokes. 42. 

HAMBURGER (L.). On centres of luminescence and variations of the gas 
pressure in spectrum tubes at electrical discharges. II. 463. . 

HAMBURGER (R. J.). On the significance of calcium- and potassiumions 
for the artificial oedema and for the lumen of the bloodvessels. 145. 

Hetium (Further experiments with liquid). QO. On the electric resistance of 
pure metals etc. X. Measurements concerning the electric resistance of 
thallium in the temperature field of liquid helium. 443. XI. Measure- 
ments concerning the electric resistance of ordinary lead and of 
uranium lead below 14° K. 451. 

HeERELLE (p’) (Studies on the bacteriophagus of). 31. II. 87. III. 171. 

Hervrz (G.). On the mean free path of slow electrons in neon and argon. 90. 

— On the excitation and ionization potentials of neon and argon. 179. 
Appendix. 442. 
— On the separation of gas mixtures by diffusion in a flowing gas. 434. 

Heux (J. W. N. Le). Explanation of some interference-curves of uni-axial 
and bi-axial crystals by superposition of elliptic pencils. III. 81. 

Ho.LttueMaAN (A. F.). Monochloro-trinitrobenzenes. 223. 

HorisBa (SHINKICH1). Determination of the vapour pressure of metallic 
arsenic. 387. 

HyDROGEN ION CONCENTRATION (The influence of) upon the action of the 
amylase of Aspergillus niger. On 

H1IJMANS VAN DEN BERGH (A. A.) v. BERGH (A. A. HIJMANS VAN DEN). 

INFLAMMATION of the udder (Changes in milk due to sterile). 275. 

IONIZATION POTENTIALS (On the excitation and) of neon and argon. 179. 
Appendix. 442. 

JANZEN (J. W.) and L.K. Wotrr. Studies on the bacteriophagus of DD HERELLE. 
Sle 87 ale ere : 

Jona (A. W. K. bE). The biscoumaric acids. 175. 

Jone (L. E. DEN DOOREN DE) and M. W. BeElsERINCK. On bacillus poly- 
myxa. 279. 

KAMERLINGH ONNEsS (H.,) v. ONNEs (H. KAMERLINGH). 

KaRSSEN (A.) and J. M. Bisvoet. Research by means of ROntgen-rays on 
the structure of the crystals of lithium and some of its compounds with 
light elements, II. Lithium-hydride. 27. 


CONTENTS v 


KeeEsom (W. H.) and J. bE smMept. On the diffraction of R6ntgen-rays in 
liquids. 118. 

K LEWN (A. DE) and R. Maanus. A further contribution concerning the function 
of the otolithic apparatus. 256. 

KoLKMEWER (N. H.). The crystal structure of germanium. 125. 
KrauseEv (R.). Ueber einen fossilen Baumstamm von Bolang (Java), ein 
Beitrag zur Kenntnis der fossilen Flora Niederlandisch-Indiens. 9. 
Kruut (H. R.) and C.F. van Duin. Heterogeneous catalysis and the orient- 

ation of adsorbed molecules. 324. 

KuENEN (J. P.). The magneto-thermic effect according to thermodynamics.384. 

Kiur (C. A. H. von WoOLzoGEn). On the eccurrence of sulphate- 
reduction in the deeper layers of the earth. 188. 

Laar (J. J. vAN). On the heat of mixing of normal and associating liquids. 
309. 399. 

LANDSTEINER (K.). Experiments on anaphylaxis with azoproteins. 34. 

Leap (Measurements concerning the electric resistance of ordinary) and 
of uranium lead below 14° K. 451. 

Leukocytes (On the causes of the emigration of). 36. 

LicHT PATH (On the) in the general theory of relativity. 288. 

Liguips (On the diffraction of R6éntgen-rays in). 118. 

— (On the heat of mixing of normal and associating). 309. 399. 

Lirnium (Research by means of R6ntgen-rays on the structure of the crystals 
of) and some of its compounds with light elements. II. Lithium-hydride. 27. 

Lorenvrz (H. A.). On WHITTAKER’S quantum mechanism in the atom. 414. 

LUMINESCENCE (On centres of) and variations of the gas pressure in spec- 
trum tubes at electrical discharges. Il. 463. 

MacGwnus (R.) and A. pve Kien. A further contribution concerning the 
function of the otolithic apparatus. 256. 

MaANniToL (Cyclic derivatives of). 335. 

Mixk (Changes in) due to sterile inflammation of the udder. 275. 

Mot (W. E. pe). The disappearance of the diploid and triploid magnico- 
ronate narcissi from the larger cultures and the appearance in their 
place of tetraploid forms. 216. 

Mo.eEcuLEs (Heterogeneous catalysis and the orientation of adsorbed). 324. 

Mo uccas (Cuba, the Antilles and the Southern). 263. 

MONOCHLORO-TRINITROBENZENES. 223. 

Morpuo.ocy (On the) of the testis of Rana fusca Résel. 99. 

Narciss! (The disappearance of the diploid and triploid magnicoronate) 
from the larger cultures and the appearance in their place of tetraploid 
forms. 216. 

NEON AND ARGON (On the mean free path of slow electrons in). 90. 


— (On the excitation and ionization potentials of). 179. Appendix. 442. 


vi CeO NPT Een? tas 


Nerve (On the regeneration of sensitive end-corpuscles after section of 
the). 319. 

ONNEsS (H. KAMERLINGH) and W. Tun. Further experiments with liquid 
helium. QO. On the electric resistance of pure metals etc. X. Measure- 
ments concerning the electric resistance of thallium in the temperature 
field of liquid helium. 443. j 

— and W. Tuwun. Further experiments with liquid helium. R. On the 
electric resistance of pure metals etc. XI. Measurements concerning the - 
electric resistance of ordinary lead and of uranium lead below 14° 
K. 451. 

Oorprt (G. J. vAN). On the morphology of the testis of Rana fusca 
Rosel. 99. 

ORTHOGNATHISM (The problem of). 371. 

OTOLITHIC APPARATUS (A further contribution concerning the function of 
the). 256. 

PERMEABILITY (Calculations of the effective) and dielectric constant of a 
powder. 293. 

PHYLOGENETIC and ontogenetic increase of the volume of the brain in 
vertebrata. 230. : 

PLANES OF SYMMETRY (Axes of rotation and) of quadratic surfaces of revolution 
through 5, 6 and 7 given points. 61. 

Point space (Numbers of circles touching plane curves defined by represent- 
ation on). 221. 

Porassium (A connection between the spectra of ionized) and argon. I. 67. 

PorassIUMIONS (On the significance of calcium- and) for the artificial oedema 
and for the lumen of the bloodvessels. 145. 

Powper (Calculations of the effective permeability and dielectric constant 
of a). 293. 

Primates (On the significance of the supraorbital ridges in the). 16. 

PSYCHOLOGICAL and physiological phenomena (Concordance of the laws of 
some). 423. 

PyripINE (The action of sodiumamide on), and some properties of x-ami- 
nopyridine. 458. 

QuantTIzATION (A remarkable case of). 2. 

QUANTUM MECHANISM (On WHITTAKER’S) in the atom. 414. 

QvuerRipo (AR1e). On the progress of the veratrin-poisoning of the striated 
frog-muscle. 364. 

Rana Fusca (On the morphology of the testis of) Résel. 99. 

Rays (Representation of a bilinear congruence of twisted cubics on a bilinear 
congruence of). 22. 

Revativity (On the light path in the general theory of). 288. 


RESPIRATORY OSCILLATIONS (On) in the galvanogram of man. 225. 


CVO GN DEIN «‘s Vil 


ROMBURGH (P VAN) and J. H. N. van pDeER Bure. Cyclic derivatiyes of 
mannitol. 335. 

RONTGEN-RAYS (Research by means of) on the structure of the crystals of 
lithium and some of its compounds with light elements. II. Lithium- 
hydride. 27. 

— (On the diffraction of) in liquids. 118. 

RuTTEN (L.). Cuba, the Antilles and the Southern Moluccas. 263. 

SAND FLOW (Observations on the incandescent) of the valley of ten thousand 
smokes. 42. 

SCHAAKE (G.). A new method for the solution of the problem of the 
characteristics in the enumerative geometry. 113. 

SCHREINEMAKERsS (F. A. H.). In-, mono- and divariant equilibria. XXII. 341. 

SrsoL_vema (B.). On the influence of the composition of the food on the 
calcium output. 395. 

— and J. E. vaAN DER ZaNDE. Changes in milk due to sterile inflam- 
mation of the udder. 275. 

— and J.E.vaN DER ZANDE. Concerning the synthetic action of bacteria 
in the paunch of the cow. 482. 

SmMEpDT (J. DE) and W. H. Keesom. On the diffraction of R6ntgen-rays in 
liquids. 118. 

Smip Jr. (L. J.). Numbers of circles touching plane curves defined by 
representation On point space. 221. 

SODIUMAMIDE (The action of) on pyridine, and some properties of z-amino- 
pyridine. 458. 

SULPHATE-REDUCTION (On the occurrence of) in the deeper layers of the 
earth. 188. 

SULPHONACETIC and ~z-sulphonpropionic acids (The dissociation constants 
of). 359. 

SUPERPOSITION (Explanation of some interference-curves of uni-axial and 
bi-axial crystals by) of elliptic pencils. III. 81. 

SUPRA-ORBITAL RIDGES (On the significance of the) in the primates. 16. 

SYNTHETIC ACTION of bacteria (Concerning the) in the paunch of the cow. 482. 

TEN THOUSAND SMOKES (Observations on the incandescent sand flow of the 
valley of). 42. 

THALLIUM (Measurements concerning the electric resistance of) in the temper- 
ature field of liquid helium. 443. 

THERMODYNAMIC QUANTITIES (The influence of a catalyst on the) regulating 
the velocity of a reaction. 199. 

THERMODYNAMICS (The magneto-thermic effect according to). 384. 

THIEL (E. VAN). The influence of a catalyst on the thermodynamic quanti- 
ties regulating the velocity of a reaction. 199. 


> 


Torrebo (A contribution to the physiology of the electrical organ of). 131. 


Vill CONTENTS 


Tuun (W.) and H. KAMERLINGH ONNEs. Further experiments with liquid 

* helium. QO. On the electric resistance of pure metals etc. X. Measure- 

ments concerning the electric resistance of thallium in the temperature 
field of liquid helium. 443. 

— and H. KaMERLINGH ONNgEs. Further experiments with liquid helium. 
R. On the electric resistance of pure metals etc. XI. Measurements 
concerning the electric resistance of ordinary lead and of uranium 
lead below 14° K. 451. 

TwisTtED cuBics (Representation of a bilinear congruence of) on a bilinear 
congruence of rays. 22. 
V eEN(H.J. van). Axes of rotation of quadratic surfaces through 4 given points.52. 

— Axes of rotation and planes of symmetry of quadratic surfaces of 
revolution through 5, 6 and 7 given points. 61. 

VERATRIN-POISONING (On the progress of the) cf the striated frog-muscle. 364. 

VERTEBRATA (Phylogenetic and ontogenetic increase of the volume of the 
brain in). 230. 

WaAERDEN (B. L. VAN DER). Ueber Determinanten aus Formenkoeff- 
zienten. 354. 

WEINBERG (A. A,). On respiratory oscillations in the galvanogram of man. 225. 

WEITZENBOCK (R.). Ueber Wirkungsfunktionen. 166. 

Went (F. A. F. C.). On a new clinostat after DE BouTrErR. 475. 

WHITTAKER’S quantum mechanism in the atom (On). 414. 

Wisaut (J. P.) and ExvisasetH DINGEMANSE. The action of sodiumamide 
on pyridine, and some properties of x-aminopyridine. 458. 

WieRSMA (E. D.). Concordance of the laws of some psychological and 
physiological phenomena. 423. 

Wotrr (L. K.) and J. W. JANZEN. Studies on the bacteriophagus of 
p'HERELLE. 31. II. 87. Ill. 171. 

Wotvius (R. J.). An objective method for determining the coagulation- 
time of blood. 127. 

WoLZOGEN Kiinr (C. A. H. von) y. Kiinr (C. A. H. von WOLZOGEN). 

W ouDE (W. VAN DER). On the light path in the general theory of relativity. 288. 

ZANDE (J. E. VAN DER) and B. SJOLLEMA. Changes in milk due to sterile 
inflammation of the udder. 275. 

— and B. SjoitLemMa. Concerning the synthetic action of bacteria in the 
paunch of the cow. 482. 

ZEEMAN (P.) and H. W. J. Dix. A connection between the spectra of 
ionized potassium and argon. I. 67. 


ZW AARDEMAKER (H.). On the alpha-automaticity of the autonomous organs. 152. 


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